JP5954017B2 - Liquid crystal compound having perfluoroalkyl chain, liquid crystal composition and liquid crystal display device - Google Patents

Description

  The present invention relates to a novel liquid crystal compound, a liquid crystal composition, and a liquid crystal display device. Specifically, it is a liquid crystal compound having a liquid crystal phase despite having no ring structure, a high clearing point, good compatibility with other compounds, a small viscosity, and a liquid crystal composition containing this compound. A liquid crystal display device using this composition can be used in a wide temperature range, can be driven at a low voltage, and can obtain a large contrast ratio and steep electro-optical characteristics.

  Liquid crystal display elements using liquid crystal compounds are widely used in displays such as watches, calculators, and personal computers. In the liquid crystal display element, the classification based on the operation mode of the liquid crystal is as follows: PC (phase change), TN (twisted nematic), STN (super twisted nematic), BTN (bistable twisted nematic), ECB (electrically refractory bicyclic conjugated). These include optically compensated bend (IPS), in-plane switching (IPS), vertical alignment (VA), and polymer sustained alignment (PSA). The classification based on the driving method of the element is PM (passive matrix) and AM (active matrix). PM (passive matrix) is classified into static and multiplex, and AM is classified into TFT (thin film transistor) and MIM (metal insulator metal).

The liquid crystal display element contains a liquid crystal composition having appropriate physical properties. In order to improve the characteristics of the device, the composition preferably has appropriate physical properties. General physical properties necessary for the liquid crystal compound as a component of the composition are as follows.
(1) being chemically stable and physically stable;
(2) having a high clearing point (liquid crystal phase-isotropic phase transition temperature);
(3) The lower limit temperature of the liquid crystal phase (nematic phase, smectic phase, etc.) is low,
(4) Excellent compatibility with other compounds,
(5) low viscosity,
It is.

  When a composition containing a chemically and physically stable liquid crystal compound as in (1) is used for a liquid crystal display element, the voltage holding ratio can be increased.

  Since the composition containing a compound having a high clearing point or a low lower limit temperature of the liquid crystal phase as in (2) and (3) has a wide nematic phase temperature range, the device can be used in a wide temperature range. .

  The liquid crystal compound is generally used as a liquid crystal composition prepared by mixing with many other liquid crystal compounds in order to develop characteristics that are difficult to be exhibited by a single compound. Therefore, the liquid crystal compound used in the device preferably has good compatibility with other compounds as in (4).

  The response speed of the device correlates with the viscosity of the liquid crystal composition. Therefore, in order to produce a device capable of responding at high speed, a composition having a low viscosity must be used. In order to reduce the viscosity of the composition, a liquid crystal compound having a high clearing point and a low viscosity is used as a viscosity reducing agent. Therefore, a liquid crystal compound having a low viscosity as in (5) is required.

  In general, the clearing point and the viscosity of a liquid crystal compound correlate with the number of ring structures constituting the compound. That is, the greater the number of rings, the higher the clearing point, but the greater the viscosity. Conversely, the smaller the number of rings, the lower the clearing point, but the lower the viscosity. Therefore, development of a compound having a liquid crystal phase and a high clearing point although it does not have a ring structure is demanded.

  So far, compounds having a perfluoroalkyl chain have been found as compounds having a liquid crystal phase despite having no ring structure. For example, Non-Patent Documents 1 to 9 show linear compounds (S-1) and (S-2) in which a perfluoroalkyl chain and an alkyl chain are linked. However, these compounds have very low compatibility with other compounds, and the upper limit temperature when added to the composition is not sufficiently high, so they are used as components of liquid crystal compositions for liquid crystal display elements. There is no example.

  Patent Documents 1 and 2 disclose linear compounds (S-3) to (S-5) having an alkyl chain or an alkenyl chain at both ends of the perfluoroalkyl chain. However, since these compounds do not have a liquid crystal phase and the upper limit temperature when added to the composition is not sufficiently high, the temperature range that can be used as a liquid crystal display device is not sufficiently wide.

German Patent Application Publication No. 4034123 German Patent Application Publication No. 10018086

Macromolecules, 1984, 17, 2786 Mol. Cryst. Liq. Cryst. Lett. 1985, 2 (3-4), 111 Macromolecules, 1986, 19, 1135 Mol. Cryst. Liq. Cryst., 1989, 168, 63 Mol. Cryst. Liq. Cryst., 1996, 281, 123 Mol. Cryst. Liq. Cryst., 1997, 302, 369 J. Fluor. Chem., 2005, 126, 79 Macromolecules, 2006, 39, 5836 Mol. Cryst. Liq. Cryst., 2006, 460, 63

  The first object of the present invention is to have a liquid crystal phase despite having no ring structure, high clearing point, good compatibility with other compounds, small viscosity, and high stability against heat, light, etc. It is providing the liquid crystal compound which has this. The second object is to provide a liquid crystal composition containing this compound and having a wide temperature range of the liquid crystal phase, a large dielectric anisotropy, a large refractive index anisotropy, a low threshold voltage, and a small viscosity. It is. A third object is to provide a liquid crystal display element containing this composition, usable in a wide temperature range, capable of being driven at a low voltage, having a large contrast ratio, and steep electro-optical characteristics. .

  The present invention provides the following liquid crystal compound, liquid crystal composition, and liquid crystal display device containing the liquid crystal composition. In addition, preferred examples of the terminal chain and the perfluoroalkyl chain in the compound represented by the formula (1) are also described below.

式（１）において、Ｒ^１は炭素数４〜１５のアルキル、−（ＣＨ_２）_２−ＣＨ＝ＣＨ_２、−（ＣＨ_２）_２−ＣＨ＝ＣＨＣＨ_３、−（ＣＨ_２）_４−ＣＨ＝ＣＨ_２、または−（ＣＨ_２）_４−ＣＨ＝ＣＨＣＨ_３であり、Ｒ^２は炭素数２〜１５のアルキル、または炭素数２〜１５のアルケニルであり、ｎは８、９、１０、１１、または１２であり、Ｒ^１およびＲ^２は同じ炭素数の直鎖アルキルになることはない。 [1] A compound represented by formula (1).

In Formula (1), R ¹ is alkyl having 4 to 15 carbon atoms, — (CH ₂ ) ₂ —CH═CH ₂ , — (CH ₂ ) ₂ —CH═CHCH ₃ , — (CH ₂ ) ₄ —CH═. CH ₂ , or — (CH ₂ ) ₄ —CH═CHCH ₃ , R ² is alkyl having 2 to 15 carbons or alkenyl having 2 to 15 carbons, and n is 8, 9, 10, 11, Or 12, and R ¹ and R ² do not become linear alkyl having the same carbon number.

[2] In the formula (1), R ¹ is alkyl having 4 to 10 carbon atoms, — (CH ₂ ) ₂ —CH═CH ₂ , — (CH ₂ ) ₂ —CH═CHCH ₃ , — (CH ₂ ) ₄ -CH = CH ₂ or, _{- (CH} 2) a 4 -CH = CHCH _3, the compounds according to claim [1] ^{R 2} is alkenyl alkyl or 2 to 10 carbon atoms, from 2 to 10 carbon atoms .

[3] In Formula (1), R ¹ is alkyl having 4 to 10 carbon atoms, — (CH ₂ ) ₂ —CH═CH ₂ , or — (CH ₂ ) ₂ —CH═CHCH ₃ , and R ² is alkyl of 2 to 10 carbon _{atoms, -CH = CH 2, -CH =} CHCH 3, -CH 2 CH = CH 2, -CH 2 CH = CHCH 3, - (CH 2) 2 -CH = CH 2 or - The compound according to item [1], wherein (CH ₂ ) ₂ —CH═CHCH ₃ .

[4] In Formula (1), R ¹ is alkyl having 4 to 10 carbon atoms, — (CH ₂ ) ₂ —CH═CH ₂ , or — (CH ₂ ) ₂ —CH═CHCH ₂ , and R ² is alkyl of 2 to 10 carbon _{atoms, -CH = CH 2, -CH =} CHCH 3, -CH 2 CH = CH 2, -CH 2 CH = CHCH 3, - (CH 2) 2 -CH = CH 2 or - The compound according to item [1], wherein (CH ₂ ) ₂ —CH═CHCH ₃ , n is 8, 9, or 10, and R ¹ ≠ R ² .

[5] The compound according to item [4], wherein n is 8 in formula (1) according to item [1].

[6] The compound according to item [5], wherein in formula (1) according to item [1], R ¹ is alkyl having 4 to 10 carbons and R ² is alkyl having 2 to 7 carbons.

[7] In the formula (1) according to the item [1], R ¹ is alkyl having 4 to 10 carbon atoms, and R ² is —CH═CH ₂ , —CH═CHCH ₃ , —CH ₂ CH═CH. _{2, -CH 2 CH = CHCH 3} , - (CH 2) 2 -CH = CH 2 or, _{- (CH} 2) compound according to Item [5] is 2 -CH = CHCH _3.

[8] In the formula (1) described in the item [1], R ¹ is — (CH ₂ ) ₂ —CH═CH ₂ , or — (CH ₂ ) ₂ —CH═CHCH ₃ , and R ² is — _{CH = CH 2, -CH = CHCH} 3, -CH 2 CH = CH 2, -CH 2 CH = CHCH 3, - (CH 2) 2 -CH = CH 2 _{or, - (CH 2) 2 -CH} = CHCH _3. The compound according to item [5], which is ₃ .

[9] A liquid crystal composition comprising at least one compound according to any one of items [1] to [8].

式（２）〜（４）において、Ｒ^３は独立して、炭素数１〜１０のアルキルまたは炭素数２〜１０のアルケニルであり、アルキルおよびアルケニルにおいて少なくとも１つの水素はフッ素で置き換えられてもよく、少なくとも１つの−ＣＨ_２−は−Ｏ−で置き換えられてもよく；Ｘ^１は、フッ素、塩素、−ＯＣＦ_３、−ＯＣＨＦ_２、−ＣＦ_３、−ＣＨＦ_２、−ＣＨ_２Ｆ、−ＣＦ＝ＣＦ_２、−ＯＣＦ_２ＣＨＦ_２、または−ＯＣＦ_２ＣＨＦＣＦ_３であり；環Ａ^１、環Ａ^２、および環Ａ^３は独立して、１，４−シクロヘキシレン、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、テトラヒドロピラン−２，５−ジイル、１，４−フェニレン、２−フルオロ−１，４−フェニレン、３−フルオロ−１，４−フェニレン、または３，５−ジフルオロ−１，４−フェニレンであり；Ｚ^１およびＺ^２は独立して、−（ＣＨ_２）_２−、−（ＣＨ_２）_４−、−ＣＯＯ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＨ_２Ｏ−、または単結合であり；Ｌ^１およびＬ^２は独立して、水素またはフッ素である。 [10] The liquid crystal composition according to item [9], further comprising at least one compound selected from the group of compounds represented by formulas (2) to (4).

In the formulas (2) to (4), R ³ is independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one hydrogen may be replaced by fluorine. Well, at least one —CH ₂ — may be replaced by —O—; X ¹ is fluorine, chlorine, —OCF ₃ , —OCHF ₂ , —CF ₃ , —CHF ₂ , —CH ₂ F, — CF ₌ CF 2, be -OCF ₂ CHF ₂ or -OCF ₂ CHFCF _3,; ring ^{A 1,} ring ^{A 2,} and ring ^{A 3} are independently 1,4-cyclohexylene, 1,3-dioxane - 2,5-diyl, pyrimidine-2,5-diyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phen Nylene, or 3,5-difluoro-1,4-phenylene; Z ¹ and Z ² are independently — (CH ₂ ) ₂ —, — (CH ₂ ) ₄ —, —COO—, —CF _2. O—, —OCF ₂ —, —CH═CH—, —C≡C—, —CH ₂ O—, or a single bond; L ¹ and L ² are independently hydrogen or fluorine.

式（５）において、Ｒ^４は、炭素数１〜１０のアルキルまたは炭素数２〜１０のアルケニルであり、アルキルおよびアルケニルにおいて、少なくとも１つの水素はフッ素で置き換えられてもよく、少なくとも１つの−ＣＨ_２−は−Ｏ−で置き換えられてもよく；Ｘ^２は−Ｃ≡Ｎまたは−Ｃ≡Ｃ−Ｃ≡Ｎであり；環Ｂ^１、環Ｂ^２、および環Ｂ^３は独立して、１，４−シクロヘキシレン、少なくとも１つの水素がフッ素で置き換えられてもよい１，４−フェニレン、１，３−ジオキサン−２，５−ジイル、テトラヒドロピラン−２，５−ジイル、またはピリミジン−２，５−ジイルであり；Ｚ^３は、−（ＣＨ_２）_２−、−ＣＯＯ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−Ｃ≡Ｃ−、−ＣＨ_２Ｏ−、または単結合であり；Ｌ^３およびＬ^４は独立して、水素またはフッ素であり；ｒは、０、１または２であり、ｓは０または１であり、ｒとｓの和は、０、１、２または３である。 [11] The liquid crystal composition according to item [9], further containing at least one compound selected from the group of compounds represented by formula (5).

In Formula (5), R ⁴ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in alkyl and alkenyl, at least one hydrogen may be replaced with fluorine, and at least one — CH ₂ — may be replaced by —O—; X ² is —C≡N or —C≡C—C≡N; Ring B ¹ , Ring B ² , and Ring B ³ are independently 1,4-cyclohexylene, 1,4-phenylene, 1,3-dioxane-2,5-diyl, tetrahydropyran-2,5-diyl, or pyrimidine-2 in which at least one hydrogen may be replaced by fluorine Z ³ is — (CH ₂ ) ₂ —, —COO—, —CF ₂ O—, —OCF ₂ —, —C≡C—, —CH ₂ O—, or a single bond Yes; L ³ and L ⁴ Is independently hydrogen or fluorine; r is 0, 1 or 2, s is 0 or 1, and the sum of r and s is 0, 1, 2 or 3.

式（６）〜（１１）において、Ｒ^５およびＲ^６は独立して、炭素数１〜１０のアルキルまたは炭素数２〜１０のアルケニルであり、アルキルおよびアルケニルにおいて、少なくとも１つの水素はフッ素で置き換えられてもよく、少なくとも１つの−ＣＨ_２−は−Ｏ−で置き換えられてもよく；環Ｃ^１、環Ｃ^２、環Ｃ^３、および環Ｃ^４は独立して、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、少なくとも１つの水素がフッ素で置き換えられてもよい１，４−フェニレン、テトラヒドロピラン−２，５−ジイル、テトラヒドロピラン−３，６−ジイル、またはデカヒドロ−２，６−ナフタレンであり；Ｚ^４、Ｚ^５、Ｚ^６、およびＺ^７は独立して、−（ＣＨ_２）_２−、−ＣＯＯ−、−ＣＨ_２Ｏ−、−ＯＣＦ_２−、−ＯＣＦ_２（ＣＨ_２）_２−、または単結合であり；Ｌ^５およびＬ^６は独立して、フッ素または塩素であり；ｔ、ｕ、ｖ、ｗ、ｘ、およびｙは独立して０または１であり、ｕ、ｖ、ｗ、およびｘの和は、１または２である。 [12] The liquid crystal composition according to item [9], further comprising at least one compound selected from the group of compounds represented by formulas (6) to (11).

In the formulas (6) to (11), R ⁵ and R ⁶ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one hydrogen is fluorine. And at least one —CH ₂ — may be replaced by —O—; Ring C ¹ , Ring C ² , Ring C ³ , and Ring C ⁴ are independently 1,4-cyclohex Silene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, tetrahydropyran-3,6-diyl, or decahydro-2 in which at least one hydrogen may be replaced by fluorine , be a ^{6-naphthalene; Z 4, Z 5, Z} 6, and ^{Z 7} are _{independently, - (CH 2) 2 -} , - COO -, - CH 2 O -, - OCF 2 -, _{OCF 2 (CH 2) 2 -} , or a single bond; ^{L 5} and ^{L 6} are independently fluorine or chlorine; t, u, v, w , x, and y are independently 0 or 1 And the sum of u, v, w, and x is 1 or 2.

式（１２）〜（１４）において、Ｒ^７およびＲ^８は独立して、炭素数１〜１０のアルキルまたは炭素数２〜１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの−ＣＨ_２−は−Ｏ−で置き換えられてもよく；環Ｄ^１、環Ｄ^２、および環Ｄ^３は独立して、１，４−シクロヘキシレン、ピリミジン−２，５−ジイル、１，４−フェニレン、２−フルオロ−１，４−フェニレン、３−フルオロ−１，４−フェニレン、または２，５−ジフルオロ−１，４−フェニレンであり；Ｚ^８およびＺ^９は独立して、−Ｃ≡Ｃ−、−ＣＯＯ−、−（ＣＨ_２）_２−、−ＣＨ＝ＣＨ−、または単結合である。 [13] The liquid crystal composition according to item [9], further containing at least one compound selected from the group of compounds represented by formulas (12) to (14).

In the formulas (12) to (14), R ⁷ and R ⁸ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH ₂ -May be replaced by -O-; Ring D ¹ , Ring D ² , and Ring D ³ are independently 1,4-cyclohexylene, pyrimidine-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z ⁸ and Z ⁹ are independently —C≡C— _{, -COO -, - (CH 2} ) 2 -, - CH = CH-, or a single bond.

[14] The liquid crystal composition according to item [10], further comprising at least one compound selected from the group of compounds represented by formula (5) according to item [11].

[15] The liquid crystal composition according to item [10], further comprising at least one compound selected from the group of compounds represented by formulas (12) to (14) according to item [13].

[16] The liquid crystal composition according to item [11], further comprising at least one compound selected from the group of compounds represented by formulas (12) to (14) according to item [13].

[17] The liquid crystal composition according to item [12], further comprising at least one compound selected from the group of compounds represented by formulas (12) to (14) according to item [13].

[18] The liquid crystal composition according to any one of items [9] to [17], further containing at least one optically active compound.

[19] The liquid crystal composition according to any one of items [9] to [18], further containing at least one antioxidant and / or ultraviolet absorber.

[20] A liquid crystal display device comprising the liquid crystal composition according to any one of items [9] to [19].

The usage of terms in the present invention is as follows. A liquid crystal compound is a generic term for a compound having a liquid crystal phase such as a nematic phase or a smectic phase and a compound having no liquid crystal phase but useful as a component of a liquid crystal composition. A liquid crystal compound, a liquid crystal composition, and a liquid crystal display element may be abbreviated as a compound, a composition, and an element, respectively. A liquid crystal display element is a general term for a liquid crystal display panel and a liquid crystal display module. The upper limit temperature of the nematic phase is a nematic phase-isotropic phase transition temperature, and may simply be abbreviated as clearing point or upper limit temperature. The lower limit temperature of the nematic phase may simply be abbreviated as the lower limit temperature. The compound represented by formula (1) may be abbreviated as compound (1). This abbreviation may also apply to compounds represented by formula (2) and the like. In the formulas (2) to (14), symbols such as A ¹ , B ¹ , and C ¹ surrounded by hexagons correspond to the ring A ¹ , the ring B ¹ , the ring C ^{1, and the} like, respectively. A plurality of the same symbols such as ring A ¹ , ring B ² and R ³ are described in the same formula or different formulas, but any two of these may be the same or different. The amount of the compound expressed as a percentage is a weight percentage (% by weight) based on the total weight of the composition.
The expression “A and / or B” means that the selection “A and B” and the selection “A or B” can be made arbitrarily.

“At least one” in “may be replaced” indicates that not only the position but also the number is arbitrary. The expression “at least one A may be replaced by B, C or D” means that any A is replaced by B, any A is replaced by C, and any A is D In addition to being replaced, it is meant to include the case where a plurality of A is replaced by at least two of B to D. For example, alkyl in which at least one —CH ₂ — may be replaced by —O— or —CH═CH— includes alkyl, alkenyl, alkoxy, alkoxyalkyl, alkoxyalkenyl, alkenyloxyalkyl. In the present invention, it is not preferable that two consecutive —CH ₂ — are replaced with —O— to become —O—O—. In addition, it is not preferable that the terminal —CH ₂ — in alkyl is replaced by —O—. The present invention is further described below.

  The liquid crystal compound of the present invention has a liquid crystal phase despite having no ring structure, and has a high clearing point, good compatibility with other compounds, small viscosity, and high stability against heat, light, etc. . The liquid crystal composition of the present invention contains this compound, and has a high maximum temperature of the nematic phase, a low minimum temperature of the nematic phase, a large dielectric anisotropy, a large refractive index anisotropy, a low threshold voltage, and a small viscosity. Have The liquid crystal display element of the present invention contains this composition and has a wide temperature range that can be used, a low driving voltage, a small power consumption, a large contrast ratio, and steep electro-optical characteristics.

1. Compound of the Present Invention The first aspect of the present invention relates to a compound represented by the formula (1).

In Formula (1), R ¹ is alkyl having 4 to 15 carbon atoms, — (CH ₂ ) ₂ —CH═CH ₂ , — (CH ₂ ) ₂ —CH═CHCH ₃ , — (CH ₂ ) ₄ —CH═. CH ₂ , or — (CH ₂ ) ₄ —CH═CHCH ₃ , and R ² is alkyl having 2 to 15 carbons or alkenyl having 2 to 15 carbons. Alkyl and alkenyl may be linear or branched, but is preferably linear. Even a branched group is preferred when it is optically active. The preferred configuration of —CH═CH— in alkenyl depends on the position of the double bond. _{-CH = CHCH 3, -CH = CHC} 2 H 5, -CH = CHC 3 H 7, -CH = CHC 4 H 9, - (CH 2) 2 -CH = CHCH 3, and - _{(CH 2) 2} - In an alkenyl having a double bond at an odd position such as CH═CHC ₂ H ₅ , a trans configuration is preferable. -CH ₂ CH ₌ CHCH _3, cis configuration in the alkenyl having an even position to the double bond, such as _{-CH 2 CH = CHC 2 H 5} , and _-CH 2 CH = _CHC 3 _{H 7} are preferred. An alkenyl compound having a preferred configuration has a high maximum temperature or a wide temperature range of the liquid crystal phase. Mol. Cryst. Liq. Cryst. , 1985, 131, 109 and Mol. Cryst. Liq. Cryst. , 1985, 131, 327.

Specific examples of _{alkyl, -C 2 H 5, -C 3} H 7, -C 4 H 9, -C 5 H 11, -C 6 H 13, -C 7 H 15, -C 8 H 17, _{-C 9 H 19, -C 10 H} 21, -C 11 H 23, -C 12 H 25, -C 13 H 27, -C 14 H 29, -C 15 H 31, -CH (CH 3) 2, _{-CH (CH 3) C 2 H} 5, -CH (CH 3) C 4 H 9, -CH (CH 3) C 6 H 13, -CH 2 CH (CH 3) 2, -CH 2 CH (CH 3 _{) C 3 H 7, -CH 2} CH (CH 3) C 5 H 11, - (CH 2) 2 -CH (CH 3) C 2 H 5, - (CH 2) 2 -CH (CH 3) C 4 _{H 9, - (CH 2)} 3 -CH (CH 3) 2, - (CH 2) 4 -CH (CH 3) C 2 H 5, Contact Beauty _{- (CH 2) 5 CH (} CH 3) _2.

Specific examples of alkenyl _{include, -CH = CH 2, -CH =} CHCH 3, -CH 2 CH = CH 2, -CH = CHC 2 H 5, -CH 2 CH = CHCH 3, - (CH 2) 2 _{-CH = CH 2, -CH = CHC} 3 H 7, -CH 2 CH = CHC 2 H 5, - (CH 2) 2 -CH = CHCH 3, - (CH 2) 3 -CH = CH 2, - ( _{CH 2) 4 -CH = CH 2} , - (CH 2) 4 -CH = CHCH 3, - (CH 2) 5 -CH = CH 2, -CH (CH 3) CH 2 CH = CH 2, -CH ( _{CH 3) CH 2 CH = CHCH} 3, -CH 2 CH (CH 3) CH = CH 2, and _{- (CH 2) 2 -CH (} CH 3) a CH = CH _2.

Preferred examples of R ¹ include alkyl having 4 to 10 carbon atoms, — (CH ₂ ) ₂ —CH═CH ₂ , — (CH ₂ ) ₂ —CH═CHCH ₃ , — (CH ₂ ) ₄ —CH═CH _2. And — (CH ₂ ) ₄ —CH═CHCH ₃ . Further, more preferable examples of R ¹ are alkyl having 4 to 10 carbon atoms, — (CH ₂ ) ₂ —CH═CH ₂ , and — (CH ₂ ) ₂ —CH═CHCH ₃ .

Preferred examples of R ² are alkyl having 2 to 10 carbons and alkenyl having 2 to 10 carbons. Further, more preferable examples of R ² include alkyl having 2 to 10 carbon atoms, —CH═CH ₂ , —CH═CHCH ₃ , —CH ₂ CH═CH ₂ , —CH ₂ CH═CHCH ₃ , — (CH ₂ ) ₂ —CH═CH ₂ and — (CH ₂ ) ₂ —CH═CHCH ₃ .

R ¹ and R ² cannot be linear alkyl having the same carbon number at the same time.

  In the formula (1), n is 8, 9, 10, 11, or 12. Preferred n is 8, 9, or 10. More preferably n is 8.

[Properties of Compound of the Present Invention and Preparation Method Thereof]
Compound (1) will be described in further detail. Compound (1) is a linear compound having a perfluoroalkyl chain. This compound is physically and chemically stable under conditions in which the device is normally used, and can provide a composition that is stable under conditions in which the device is normally used. This compound has good compatibility with other compounds, and even when this composition is stored at a low temperature, this compound does not precipitate as crystals (or a smectic phase). Although this compound does not have a ring structure, it has a liquid crystal phase and has a high clearing point, so that a composition having a high maximum temperature of the liquid crystal phase can be provided. Furthermore, since this compound has a low viscosity, it can be used as a thickener for the composition, and is suitable for producing a device capable of responding at high speed.

It is possible to arbitrarily adjust physical properties such as clearing point, compatibility with other compounds, and viscosity by appropriately selecting the types of R ¹ and R ² and combinations thereof, and the number of n in compound (1). Is possible. The effects of this type and combination on the physical properties of compound (1) will be described below.

When R ¹ and R ² are linear, the temperature range of the liquid crystal phase is wide and the viscosity is small. When R ¹ or R ² is a branched chain, the compatibility with other compounds is good. A compound in which R ¹ or R ² is an optically active group is useful as a chiral dopant. By adding this compound to the composition, a reverse twisted domain generated in the device can be prevented. Compounds in which R ¹ and R ² are not optically active groups are useful as components of the composition.

When R ¹ is alkyl, the compatibility with other compounds improves as the carbon number increases, and the clearing point also improves. When R ¹ is — (CH ₂ ) ₂ —CH═CH ₂ or — (CH ₂ ) ₄ —CH═CH ₂ , the compatibility with other compounds is good and the viscosity is small. When R ¹ is — (CH ₂ ) ₂ —CH═CHCH ₃ or — (CH ₂ ) ₄ —CH═CHCH ₃ , the clearing point is high, and the upper limit temperature of the liquid crystal phase when the composition is formed is high. .

When R ² is alkyl, the compatibility with other compounds improves as the carbon number increases, and the clearing point also improves. When R ² is —CH═CH ₂ , the viscosity is particularly small. When R ² is — (CH ₂ ) ₂ —CH═CH ₂ , the compatibility with other compounds is good and the viscosity is small. When R ² is —CH ₂ CH═CHCH ₃ or — (CH ₂ ) ₂ —CH═CHCH ₃ , the clearing point is high, and the upper limit temperature of the liquid crystal phase when the composition is formed is high.

When R ¹ and R ² are both alkyl, the stability of the compound is particularly high. However, R ¹ and R ² do not become linear alkyl having the same carbon number at the same time. When R ¹ is alkyl and R ² is alkenyl, the compatibility with other compounds is good and the viscosity is small. When R ¹ is — (CH ₂ ) ₂ —CH═CH ₂ , or — (CH ₂ ) ₂ —CH═CHCH ₃ , and R ² is alkenyl, the clearing point is high. The upper limit temperature of the liquid crystal phase is high.

  As n increases, the clearing point improves and the upper limit temperature of the composition is improved. When n is 8, 9, or 10, the compatibility with other compounds is good and the viscosity is small. When n is 11 or 12, the clearing point is high and the temperature range of the liquid crystal phase is wide.

As described above, a compound having desired physical properties can be obtained by appropriately selecting the types and combinations of R ¹ and R ² and the number of n. Therefore, the compound (1) is useful as a component of a composition used for devices such as PC, TN, STN, ECB, OCB, IPS, and VA.

[Synthesis of Compound (1)]
Next, the synthesis of compound (1) will be described. Compound (1) can be synthesized by appropriately combining techniques in organic synthetic chemistry.

これらの式において、Ｒ^７は炭素数２〜１３のアルキルであり、Ｒ^８は炭素数１〜１３のアルキル、または水素であり、Ｒ^７が直鎖アルキルである場合には、Ｒ^７≠Ｒ^８であり、ｎは８、９、１０、１１、または１２である。 [Method of synthesizing compound (1)]
There are a plurality of methods for synthesizing the compound represented by the formula (1), and examples thereof are shown here. Among the compounds represented by the formula (1), when R ¹ and R ² are both alkyl, they can be synthesized by the following method. Diiodoperfluoroalkane (15) and alkene (16) are reacted under radical generating conditions such as sodium dithinite and sodium bicarbonate to give monoalkyl adduct (17). Subsequently, the alkene (18) is reacted under radical generating conditions to obtain the dialkyl adduct (19). Next, reduction with lithium aluminum hydride or the like can lead to compound (1).

In these formulas, R ⁷ is alkyl having 2 to 13 carbon atoms, R ⁸ is alkyl having 1 to 13 carbon atoms, or hydrogen, and when R ⁷ is linear alkyl, R ⁷ ≠ R ⁸ and n is 8, 9, 10, 11, or 12.

これらの式において、Ｒ^７は炭素数２〜１３のアルキルであり、ｎは８、９、１０、１１、または１２である。 In the formula (1), when R ¹ is alkyl and R ² is propyl, it can also be synthesized by the following method. The monoalkyl adduct (17) and allyl bromide (20) are reacted under radical generating conditions to obtain the allyl adduct (21). Subsequent reduction using Raney nickel or the like can lead to compound (1).

In these formulas, R ⁷ is alkyl having 2 to 13 carbons, and n is 8, 9, 10, 11, or 12.

これらの式において、Ｒ^７は炭素数２〜１３のアルキルであり、Ｒ^８は炭素数１〜１３のアルキル、または水素であり、ｎは８、９、１０、１１、または１２である。 In the formula (1), when R ¹ is alkyl and R ² is 1-alkenyl, it can be synthesized by the following method. Chloroiodoperfluoroalkane (22) and alkene (18) are reacted under radical generating conditions to obtain monoalkyl adduct (23). Subsequent treatment with a base such as potassium hydroxide to obtain the alkenyl derivative (24), followed by reacting the alkene (16) in the presence of sodium dithinite and sodium bicarbonate in a dimethyl sulfoxide (DMSO) solvent. Can lead to compound (1).

In these formulas, R ⁷ is alkyl having 2 to 13 carbon atoms, R ⁸ is alkyl having 1 to 13 carbon atoms, or hydrogen, and n is 8, 9, 10, 11, or 12.

これらの式において、Ｒ^７は炭素数２〜１３のアルキルであり、Ｒ^９は水素または−ＣＨ_３であり、ｎは８、９、１０、１１、または１２である。 In the formula (1), when R ¹ is alkyl and R ² is —CH ₂ CH═CH ₂ , or —CH ₂ CH═CHCH ₃ , they can be synthesized by the following method. The alkenyl bromide (25) is reacted with the monoalkyl adduct (17) under radical generating conditions to obtain the alkenyl adduct (26). Subsequently, reduction with lithium aluminum hydride or the like can lead to compound (1).

In these formulas, R ⁷ is alkyl having 2 to 13 carbon atoms, R ⁹ is hydrogen or —CH ₃ , and n is 8, 9, 10, 11, or 12.

これらの式において、Ｒ^７は炭素数２〜１３のアルキルであり、Ｒ^９は水素または−ＣＨ_３であり、ｎは８、９、１０、１１、または１２である。 In the formula (1), when R ¹ is alkyl and R ² is — (CH ₂ ) ₂ —CH═CH ₂ , or — (CH ₂ ) ₂ —CH═CHCH ₃ , they can be synthesized by the following method. The alkanol derivative (29) is obtained by reacting the monoalkyl adduct (17) with allyl alcohol (27) under radical generating conditions, followed by reduction with lithium aluminum hydride or the like. Subsequently, oxidation is performed using Dess-Martin periodinane or the like to obtain an alkyl aldehyde derivative (30), and then a Wittig reaction using the corresponding phosphonium salt (31) is performed to lead to the compound (1). Can do.

In these formulas, R ⁷ is alkyl having 2 to 13 carbon atoms, R ⁹ is hydrogen or —CH ₃ , and n is 8, 9, 10, 11, or 12.

これらの式において、Ｒ^８は炭素数１〜１３のアルキル、または水素であり、Ｒ^９は水素または−ＣＨ_３であり、ｎは８、９、１０、１１、または１２である。 In the formula (1), when R ¹ is — (CH ₂ ) ₂ —CH═CH ₂ or — (CH ₂ ) ₂ —CH═CHCH ₃ , and R ² is 1-alkenyl, the following method is used. Can be synthesized. The alkanol derivative (32) is obtained by reacting the alkenyl derivative (24) with allyl alcohol (27) in the presence of sodium dithionite and sodium hydrogen carbonate in a DMSO solvent. Subsequently, after oxidation with desmartin periodinane or the like to obtain an alkyl aldehyde derivative (33), Wittig reaction using the corresponding phosphonium salt (31) is conducted to lead to the compound (1). Can do.

In these formulas, R ⁸ is alkyl having 1 to 13 carbon atoms, or hydrogen, R ⁹ is hydrogen or —CH ₃ , and n is 8, 9, 10, 11, or 12.

これらの式において、Ｒ^９は水素または−ＣＨ_３であり、ｎは８、９、１０、１１、または１２である。 In Formula (1), R ¹ is — (CH ₂ ) ₂ —CH═CH ₂ , or — (CH ₂ ) ₂ —CH═CHCH ₃ , and R ² is CH ₂ ═CHCH ₂ —, or CH ₃ CH When = CHCH ₂ —, it can be synthesized by the following method. A dialkenyl adduct (34) is obtained by reacting diiodoperfluoroalkane (15) with alkenyl bromide (25) under radical generating conditions. Subsequently, allyl alcohol (27) is reacted under radical generating conditions, and then reduced using lithium aluminum hydride or the like to obtain alkanol derivative (36). Subsequently, after oxidation with desmartin periodinane and the like to obtain an alkyl aldehyde derivative (37), Wittig reaction using the corresponding phosphonium salt (31) is performed to lead to the compound (1). Can do.

In these formulas, R ⁹ is hydrogen or —CH ₃ and n is 8, 9, 10, 11, or 12.

これらの式において、ｎは８、９、１０、１１、または１２である。 In the formula (1), when R ¹ is — (CH ₂ ) ₂ —CH═CHCH ₃ and R ² is — (CH ₂ ) ₂ —CH═CH ₂ , they can be synthesized by the following method. Dialkanol derivative (39) is obtained by reacting diiodoperfluoroalkane (15) with allyl alcohol (27) under radical generating conditions, followed by reduction using lithium aluminum hydride or the like. Subsequently, oxidation is performed using Dess-Martin periodinane or the like to obtain a dialkylaldehyde derivative (40), and then a Wittig reaction using methyltriphenylphosphonium bromide (41) is performed to obtain an alkylaldehyde derivative (42). Get. Next, a Wittig reaction using ethyltriphenylphosphonium bromide (43) can be conducted to lead to compound (1).

In these formulas, n is 8, 9, 10, 11, or 12.

これらの式において、Ｒ^８は炭素数１〜１３のアルキル、または水素であり、Ｒ^９は水素または−ＣＨ_３であり、ｎは８、９、１０、１１、または１２である。 In the formula (1), when R ¹ is — (CH ₂ ) ₄ —CH═CH ₂ or — (CH ₂ ) ₄ —CH═CHCH ₃ , and R ² is 1-alkenyl, the following method is used. Can be synthesized. The alkanol derivative (45) is obtained by reacting the alkenyl derivative (24) with 4-penten-1-ol (44) in the presence of sodium dithinite and sodium hydrogen carbonate in a DMSO solvent. Subsequently, oxidation is performed using Dess-Martin periodinane or the like to obtain an alkyl aldehyde derivative (46), and then a Wittig reaction using the corresponding phosphonium salt (31) is performed to lead to the compound (1). Can do.

In these formulas, R ⁸ is alkyl having 1 to 13 carbon atoms, or hydrogen, R ⁹ is hydrogen or —CH ₃ , and n is 8, 9, 10, 11, or 12.

これらの式において、Ｒ^９は水素または−ＣＨ_３であり、ｎは８、９、１０、１１、または１２である。 In Formula (1), R ¹ is — (CH ₂ ) ₄ —CH═CH ₂ , or — (CH ₂ ) ₄ —CH═CHCH ₃ , and R ² is CH ₂ ═CHCH ₂ —, or CH ₃ CH When = CHCH ₂ —, it can be synthesized by the following method. A dialkenyl adduct (47) is obtained by reacting diiodoperfluoroalkane (15) with alkenyl bromide (25) under radical generating conditions. Subsequently, 4-penten-1-ol (44) is reacted under radical generating conditions and then reduced using lithium aluminum hydride or the like to obtain an alkanol derivative (49). Subsequently, after oxidation with desmartin periodinane and the like to obtain an alkyl aldehyde derivative (50), Wittig reaction using the corresponding phosphonium salt (31) is conducted to lead to the compound (1). Can do.

In these formulas, R ⁹ is hydrogen or —CH ₃ and n is 8, 9, 10, 11, or 12.

[Synthesis of Compound (15) and Compound (22) as Synthetic Raw Materials]
Diiodoperfluoroalkane (15) and chloroiodoperfluoroalkane (22), which are raw materials for synthesis of compound (1), are 1,8-diiodoperfluorooctane (15-1) in which n = 8 in each formula, And 1-chloro-8-iodoperfluorooctane (22-1) are commercially available. Other chain length compounds can be synthesized by the following method.

A compound in which n = 10 or n = 12 in the formula (15) can be synthesized by the following method. The compound (15-1) and tetrafluoroethylene (51) are reacted under high temperature and pressure conditions, and fractionated to give 1,10-diiodoperfluorodecane (15-2), 1,12-diiodo. Perfluorododecane (15-3) can be obtained. Further, 1-chloro-10-iodoperfluorodecane (22-2) and 1-chloro-12-iodoperfluorododecane (22-3) are obtained by performing the same operation using compound (22-1). Can do.

In the formula (15), a compound in which n = 9 or n = 11 is obtained by reacting commercially available 1,3-diiodoperfluoropropane (52) and tetrafluoroethylene (51) under high temperature and pressure conditions. Thus, 1,9-diiodoperfluorononane (15-4) and 1,11-diiodoperfluorodoundecane (15-5) can be obtained.

A compound in which n = 9 or n = 11 in the formula (22) is obtained by reacting commercially available perfluorocyclopropane (53) with iodine monochloride at a high temperature to give 1-chloro-3-iodoperfluoropropane (54). After being obtained, by reacting with tetrafluoroethylene (51) under high temperature and pressure conditions, 1-chloro-9-iodoperfluorononane (22-4), 1-chloro-11-iodoperfluundecane (22- 5) can be obtained.

2. Hereinafter, the liquid crystal composition of the present invention will be described. The component of the liquid crystal composition contains at least one compound (1), but may contain two or more compounds (1). Moreover, when preparing the liquid crystal composition of this invention, a component can also be selected in consideration of the viscosity of a compound (1), for example. The liquid crystal composition was selected component, low viscosity, has a large dielectric anisotropy, has a suitable elastic constant K _33, low threshold voltage, maximum temperature of a nematic phase (nematic phase -Phase transition temperature of isotropic phase) is high, and minimum temperature of nematic phase is low.

[Liquid crystal composition (1)]
The liquid crystal composition of the present invention contains the compound represented by the formula (1) of the present invention as component A. The composition of only component A or the composition of component A and other components not specifically indicated in the present specification may be used, but components B, C, D, and By adding a component selected from E, the liquid crystal composition of the present invention having various characteristics can be provided.

  The component added to component A was selected from the group consisting of at least one compound selected from the group consisting of formulas (2), (3) and (4) and / or the group consisting of formula (5). Component C comprising at least one compound and / or at least one compound selected from the group consisting of formulas (6), (7), (8), (9), (10) and (11) What mixed the component D which consists of is preferable. Further, by mixing component E consisting of at least one compound selected from the group consisting of formulas (12), (13) and (14), threshold voltage, liquid crystal phase temperature range, refractive index anisotropy, Dielectric anisotropy and viscosity can be adjusted.

  In addition, each component of the liquid crystal composition used in the present invention is not greatly different in physical properties even if it is an analog composed of an isotope element of each element.

  Among the components B, formulas (2-1) to (2-16) can be given as preferred examples of the compound represented by the formula (2), and formula (3) is a preferred example of the compound represented by the formula (3). 3-1) to (3-112) can be exemplified, and preferred examples of the compound represented by the formula (4) include formulas (4-1) to (4-54).

これらの式において、Ｒ^３およびＸ^１は前記と同じ定義である。

In these formulas, R ³ and X ¹ are as defined above.

  Since the compounds represented by the formulas (2), (3), and (4), that is, the component B has a positive dielectric anisotropy and is very excellent in thermal stability and chemical stability, It is used when preparing liquid crystal compositions for TFT and PSA. The content of component B in the liquid crystal composition of the present invention is suitably in the range of 1 to 99% by weight with respect to the total weight of the liquid crystal composition, preferably 10 to 97% by weight, more preferably 40 to 95% by weight. It is. Moreover, a viscosity can be adjusted by further containing the compound (component E) represented by Formula (12), (13), and (14).

In the formula (5), when o is 2, the two rings C ² may be the same or different. Preferred examples of the compound represented by formula (5), that is, component C, include formulas (5-1) to (5-64).

これらの式において、Ｒ^４およびＸ^２は前記と同じ定義である。

In these formulas, R ⁴ and X ² are as defined above.

  The compound represented by the formula (5), that is, the component C has a positive dielectric anisotropy and has a very large value, so that it is mainly used when preparing a liquid crystal composition for STN, TN, or PSA. By containing this component C, the threshold voltage of the composition can be reduced. Moreover, adjustment of viscosity, adjustment of refractive index anisotropy, and liquid crystal phase temperature range can be expanded. It can also be used to improve steepness.

  When preparing a liquid crystal composition for STN or TN, the content of component C is in the range of 0.1 to 99.9% by weight, preferably 10 to 97% by weight, more preferably 40 to 40%. 95% by weight. Also, the threshold voltage, liquid crystal phase temperature range, refractive index anisotropy, dielectric anisotropy, viscosity, etc. can be adjusted by mixing the components described later.

  From at least one compound selected from the group of compounds represented by formulas (6), (7), (8), (9), (10), and (11) as components to be added to component A What mixed the component D which becomes is preferable. Further, by mixing component E consisting of at least one compound selected from the group of compounds represented by formulas (12), (13) and (14), the threshold voltage, the liquid crystal phase temperature range, Refractive index anisotropy, dielectric anisotropy, viscosity and the like can be adjusted.

  Component D consisting of at least one compound selected from the group of compounds represented by formulas (6), (7), (8), (9), (10), and (11) is vertically aligned. This is a preferred component when preparing the liquid crystal composition of the present invention having a negative dielectric anisotropy used in a mode (VA mode), a polymer support alignment mode (PSA mode) and the like.

  In addition, each component of the liquid crystal composition used in the present invention is not greatly different in physical properties even if it is an analog composed of an isotope element of each element.

  As preferred examples of the compound (component D) represented by the formulas (6), (7), (8), (9), (10), and (11), the formulas (6-1) to (6-6) ), (7-1) to (7-15), (8-1), (9-1) to (9-3), (10-1) to (10-11), and (11-1) To (11-10).

これらの式において、Ｒ^５およびＲ^６は前記と同じ定義である。

In these formulas, R ⁵ and R ⁶ are as defined above.

  These compounds of component D are mainly used for liquid crystal compositions for VA mode and PSA mode having a negative dielectric anisotropy value. Increasing the content lowers the threshold voltage of the composition, but increases the viscosity. Therefore, it is preferable to reduce the content as long as the required value of the threshold voltage is satisfied. However, since the absolute value of the dielectric anisotropy is about 5, if the content is less than 40% by weight, voltage driving may not be possible.

  Since the compound represented by the formula (6) among the component D is a bicyclic compound, it has the effect of mainly adjusting the threshold voltage, adjusting the viscosity, or adjusting the refractive index anisotropy. Further, since the compounds represented by the formulas (7) and (8) are tricyclic compounds, the clearing point is increased, the nematic range is increased, the threshold voltage is decreased, and the refractive index anisotropy is increased. The effect of doing etc. is acquired. In addition, Expressions (9), (10), and (11) can provide effects such as lowering the threshold voltage.

  The content of component D is preferably 40% by weight or more, more preferably 50 to 95% by weight, based on the total amount of the composition when a composition for VA mode and PSA mode is prepared. Further, by mixing the component D, it is possible to control the elastic constant and control the voltage transmittance curve of the composition. When component D is mixed with a composition having a positive dielectric anisotropy, the content is preferably 30% by weight or less based on the total amount of the composition.

  As preferred examples of the compound (component E) represented by the formulas (12), (13) and (14), the formulas (12-1) to (12-11), (13-1) to (13-19), And (14-1) to (14-6).

これらの式において、Ｒ^７およびＲ^８は前記と同じ定義である。

In these formulas, R ⁷ and R ⁸ are as defined above.

  The compound (component E) represented by the formulas (12), (13), and (14) is a compound having a small absolute value of dielectric anisotropy and close to neutrality. The compound represented by the formula (12) is mainly effective in adjusting the viscosity or the refractive index anisotropy, and the compounds represented by the formulas (13) and (14) are nematic such as increasing the clearing point. It has the effect of widening the range or adjusting the refractive index anisotropy.

  Increasing the content of the compound represented by Component E increases the threshold voltage of the liquid crystal composition and decreases the viscosity. Therefore, as long as the required value of the threshold voltage of the liquid crystal composition is satisfied, the content is More is desirable. When preparing a liquid crystal composition for VA or PSA, the content of component E is preferably 30% by weight or more, more preferably 40% by weight or more based on the total amount of the composition.

  The liquid crystal composition of the present invention preferably contains at least one kind of the compound represented by the formula (1) of the present invention in a proportion of 0.1 to 99% by weight in order to develop excellent characteristics.

  The liquid crystal composition of the present invention is generally prepared by a known method, for example, a method in which necessary components are dissolved at a high temperature. Further, an additive well known to those skilled in the art is added depending on the application, for example, an optically active compound as described below, a polymerizable compound, a liquid crystal composition of the present invention containing a polymerization initiator, a dye A liquid crystal composition for GH type to which is added can be prepared. Usually, additives are well known to those skilled in the art and are described in detail in the literature.

  The liquid crystal composition of the present invention may further contain one or more optically active compounds in addition to the liquid crystal composition of the present invention described above.

  A known chiral dopant is added as an optically active compound. This chiral dopant has the effect of inducing the helical structure of the liquid crystal to adjust the necessary twist angle and preventing reverse twist. Examples of the chiral dopant include the following optically active compounds (Op-1) to (Op-13).

  In the liquid crystal composition of the present invention, these optically active compounds are usually added to adjust the twist pitch. The twist pitch is preferably adjusted in the range of 40 to 200 μm in the case of a liquid crystal composition for TFT and TN. If it is the liquid crystal composition for STN, it is preferable to adjust to the range of 6-20 micrometers. In the case of the bistable TN mode, it is preferably adjusted to a range of 1.5 to 4 μm. Two or more optically active compounds may be added for the purpose of adjusting the temperature dependence of the pitch.

  The liquid crystal composition of the present invention can be obtained as a GH type liquid crystal composition by adding a dichroic dye such as merocyanine, styryl, azo, azomethine, azoxy, quinophthalone, anthraquinone, and tetrazine. It can also be used.

  The liquid crystal composition of the present invention includes a microencapsulated light scattering type liquid crystal display device (NCAP) produced by microencapsulating nematic liquid crystal, and a polymer dispersion type produced by forming a three-dimensional network polymer in the liquid crystal. It can be used as a liquid crystal composition for a liquid crystal display element (PDLCD), for example, a polymer network liquid crystal display element (PNLCD), a birefringence control (ECB) type, and a DS type.

  The liquid crystal composition of the present invention can also be used as a PSA (Polymer Sustained Alignment) type liquid crystal composition by adding a polymerizable compound. Examples of polymerizable compounds are compounds having polymerizable groups such as acrylate, methacrylate, vinyl, vinyloxy, propenyl ether, epoxy, vinyl ketone, and oxetane. The polymerizable compound is preferably polymerized by UV irradiation or the like in the presence of a suitable initiator such as a photopolymerization initiator. Appropriate conditions for polymerization, the appropriate type of initiator, and the appropriate amount are known to those skilled in the art and are described in the literature. For example, Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF), or Darocur 1173 (registered trademark; BASF), which are photopolymerization initiators, are suitable for radical polymerization.

[Method for producing liquid crystal composition]
In the liquid crystal composition according to the present invention, for example, when the compound constituting each component is a liquid, the respective compounds are mixed and shaken, and when the compound includes a solid, the respective compounds are mixed. It can be prepared by making each liquid by heating and then shaking. The liquid crystal composition according to the present invention can also be prepared by other known methods.

[Characteristics of liquid crystal composition]
In the liquid crystal composition according to the present invention, the upper limit temperature of the nematic phase can be set to 70 ° C. or more, the lower limit temperature of the nematic phase can be set to −20 ° C. or less, and the temperature range of the nematic phase is wide. Therefore, a liquid crystal display element including this liquid crystal composition can be used in a wide temperature range.

  In the liquid crystal composition according to the present invention, the refractive index anisotropy can be in the range of 0.05 to 0.18 by appropriately adjusting the composition and the like.

  In the liquid crystal composition according to the present invention, the dielectric anisotropy is usually in the range of -5.0 to -2.0, preferably the dielectric anisotropy in the range of -4.5 to -2.5. A liquid crystal composition having properties can be obtained. A liquid crystal composition having a dielectric anisotropy in the range of −4.5 to −2.5 can be suitably used as a liquid crystal display element that operates in an IPS mode, a VA mode, or a PSA mode.

[Liquid crystal display element]
The liquid crystal composition according to the present invention has operation modes such as a PC mode, a TN mode, an STN mode, an OCB mode, and a PSA mode, and not only a liquid crystal display element driven by an AM mode, but also a PC mode, a TN mode, an STN mode. It can also be used for a liquid crystal display element having an operation mode such as a mode, an OCB mode, a VA mode, and an IPS mode and driven by a passive matrix (PM) method.

  These AM-type and PM-type liquid crystal display elements can be applied to any liquid crystal display such as a reflective type, a transmissive type, and a transflective type.

  In addition, the liquid crystal composition according to the present invention includes a DS (dynamic scattering) mode element using a liquid crystal composition to which a conductive agent is added, and an NCAP (nematic curvilinear aligned phase) element manufactured by microencapsulating a liquid crystal composition. Also, it can be used for a PD (polymer dispersed) element in which a three-dimensional network polymer is formed in a liquid crystal composition, for example, a PN (polymer network) element.

  In particular, since the liquid crystal composition according to the present invention has the above-described characteristics, it is driven in an operation mode using a liquid crystal composition having a negative dielectric anisotropy such as a VA mode, an IPS mode, or a PSA mode. The liquid crystal display element can be suitably used for an AM liquid crystal display element, and can be particularly suitably used for an AM liquid crystal display element driven in a VA mode.

  Note that in a liquid crystal display element driven in a TN mode, a VA mode, or the like, the direction of the electric field is perpendicular to the liquid crystal layer. On the other hand, in the liquid crystal display element driven in the IPS mode or the like, the direction of the electric field is parallel to the liquid crystal layer. Note that the structure of the liquid crystal display element driven in the VA mode is K.K. Ohmuro, S.M. Kataoka, T .; Sasaki and Y.S. Koike, SID '97 Digest of Technical Papers, 28, 845 (1997), and the structure of a liquid crystal display device driven in the IPS mode is reported in International Publication No. 91/10936 pamphlet (family: US55768867). Yes.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited by these Examples. Unless otherwise specified, “%” is “wt%”.

Since the obtained compound was identified by a nuclear magnetic resonance spectrum obtained by ¹ H-NMR analysis, a gas chromatogram obtained by gas chromatography (GC) analysis, etc., the analysis method will be described first.

¹ H-NMR analysis: DRX-500 (manufactured by Bruker BioSpin Co., Ltd.) was used as a measurement apparatus. The measurement was carried out by dissolving the sample synthesized in Examples and the like in a deuterated solvent in which a sample such as CDCl ₃ is soluble, and at room temperature under conditions of 500 MHz and 24 times of integration. In the description of the obtained nuclear magnetic resonance spectrum, s is a singlet, d is a doublet, t is a triplet, q is a quartet, and m is a multiplet. Tetramethylsilane (TMS) was used as an internal standard for chemical shift (δ).

  GC analysis: GC-14B type gas chromatograph made by Shimadzu Corporation was used as a measuring apparatus. The column was a capillary column CBP1-M25-025 (length 25 m, inner diameter 0.22 mm, film thickness 0.25 μm) manufactured by Shimadzu Corporation; dimethylpolysiloxane (nonpolar) was used as the stationary liquid phase. Helium was used as the carrier gas, and the flow rate was adjusted to 1 ml / min. The temperature of the sample vaporization chamber was set to 300 ° C., and the temperature of the detector (FID) was set to 300 ° C.

The sample was dissolved in toluene to prepare a 1% by weight solution, and 1 μl of this solution was injected into the sample vaporization chamber.
As a recorder, a C-R6A Chromatopac manufactured by Shimadzu Corporation or an equivalent thereof was used. The obtained gas chromatogram shows the peak retention time and peak area value corresponding to the component compounds.

  As a sample dilution solvent, for example, chloroform or hexane may be used. Further, as columns, Agilent Technologies Inc. Capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm), Agilent Technologies Inc. HP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Restek Corporation, length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm, SGE International Pty. BP-1 made of Ltd (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) or the like may be used.

  The area ratio of peaks in the gas chromatogram corresponds to the ratio of component compounds. In general, the weight% of the component compound of the analysis sample is not completely the same as the area% of each peak of the analysis sample. However, when the above-described column is used in the present invention, the correction factor is substantially 1. Therefore, the weight% of the component compound in the analysis sample substantially corresponds to the area% of each peak in the analysis sample. This is because there is no significant difference in the correction coefficients of the component compounds.

[Measurement sample]
There are two types of samples for measuring the physical properties of the compound: when the compound itself is used as a sample, and when the compound is mixed with a mother liquid crystal as a sample.

  When a sample in which a compound was mixed with mother liquid crystals was used, measurement was performed by the following method. First, a sample was prepared by mixing 15% by weight of the obtained compound and 85% by weight of the base liquid crystal. And the extrapolation value was computed from the measured value of the obtained sample according to the extrapolation method shown to the following formula. This extrapolated value was taken as the physical property value of this compound.

<Extrapolated value> = (100 × <Measured value of sample> − <Weight% of mother liquid crystal> × <Measured value of mother liquid crystal>) / <Weight% of compound>

  Even when the ratio of the compound to the mother liquid crystal is this ratio, when the smectic phase or crystal is precipitated at 25 ° C., the ratio of the compound to the mother liquid crystal is 10% by weight: 90% by weight, 5% by weight: 95% by weight, 1% by weight: 99% by weight in order, measuring the physical properties of the sample with a composition in which the smectic phase or crystals no longer precipitate at 25 ° C., and extrapolating the values according to the above formula This was determined as the physical property value of the compound.

There are various types of mother liquid crystals used for measurement. For example, the mother liquid crystal A can be used. The composition (% by weight) of the mother liquid crystal A is as follows.
Mother liquid crystal A:

The physical properties of the mother liquid crystal A were as follows.
Maximum temperature (T _NI ) = 100.1 ° C .; dielectric anisotropy (Δε) = 5.10; refractive index anisotropy (Δn) = 0.093; viscosity (η) = 25.6 mPa · s.

[Measuring method]
The physical properties of the compound were measured by the following method. Many of these are the methods described in the Standard of Electronic Industries Association of Japan EIAJ ED-2521A or a modified method thereof. Moreover, TFT was not attached to the TN element used for the measurement.

  Of the physical property values, when the compound itself was used as a sample, the measured value was described as data. When a mixture of a compound and mother liquid crystals was used as a sample, values calculated by extrapolation from the measured values were described as data. For the measurement of the phase structure and the phase transition temperature, the compound was used as a sample as it was. For other measurements, a mixture of the compound and mother liquid crystal A was used as a sample.

Phase structure and phase transition temperature (° C.): Measurement was performed by the following methods (1) and (2).
(1) Place a sample on a hot plate (Mettler FP-52 type hot stage) of a melting point measuring apparatus equipped with a polarizing microscope, and observe the phase state and its change with a polarizing microscope while heating at a rate of 3 ° C./min. , Identified the type of liquid crystal phase.
(2) Using a scanning calorimeter Diamond DSC system manufactured by PerkinElmer, Inc., the temperature is increased and decreased at a rate of 3 ° C./min, and the endothermic peak or the starting point of the exothermic peak accompanying the phase change of the sample is obtained by extrapolation (on set ) And the phase transition temperature was determined.

Hereinafter, the crystal is expressed as C, and when the crystal can be distinguished, it is expressed as C ₁ or C ₂ , respectively. Further, the smectic phase is represented as S and the nematic phase is represented as N. The liquid (isotropic) was designated as I. In the smectic phase, when a smectic A phase, a smectic B phase, or a smectic C phase can be distinguished, they are represented as S _A , S _B , or S _C , respectively. As a representation of the phase transition temperature, for example, “C 50.0 N 100.0 I” means that the phase transition temperature (CN) from the crystal to the nematic phase is 50.0 ° C., and the phase from the nematic phase to the liquid The transition temperature (NI) is 100.0 ° C. The same applies to other notations.

Maximum temperature of nematic phase (T _NI or NI; ° C.): A sample is placed on a hot plate (Mettler FP-52 hot stage) of a melting point measurement apparatus equipped with a polarizing microscope and heated at a rate of 1 ° C./min. While observing the polarizing microscope. The temperature at which a part of the sample changed from a nematic phase to an isotropic liquid was defined as the upper limit temperature of the nematic phase. Hereinafter, the upper limit temperature of the nematic phase may be simply abbreviated as “upper limit temperature”.

  Low temperature compatibility: Prepare a sample in which the mother liquid crystal and the compound are mixed so that the amount of the compound is 15% by weight, 10% by weight, 5% by weight, 3% by weight, and 1% by weight. Put in. The glass bottle was stored in a freezer at −10 ° C. or −20 ° C. for a certain period, and then it was observed whether a crystal or smectic phase was precipitated.

  Viscosity (bulk viscosity; η; measured at 20 ° C .; mPa · s): A sample (mixture of mother liquid crystal and compound) was measured using an E-type rotational viscometer.

  Refractive index anisotropy (Δn; measured at 25 ° C.): An Abbe refractometer in which light having a wavelength of 589 nm was used and a polarizing plate was attached to an eyepiece. After rubbing the surface of the main prism in one direction, the sample was dropped on the main prism. The refractive index (n‖) was measured when the direction of polarized light was parallel to the direction of rubbing. The refractive index (n⊥) was measured when the direction of polarized light was perpendicular to the direction of rubbing. The value of refractive index anisotropy (Δn) was calculated from the equation: Δn = n∥−n⊥.

Dielectric anisotropy (Δε; measured at 25 ° C.): A sample was put in a TN device having a distance (gap) between two glass substrates of about 9 μm and a twist angle of 80 degrees. 20 volts was applied to the cell, and the dielectric constant (ε 率) in the major axis direction of the liquid crystal molecules was measured. 0.5 V was applied, and the dielectric constant (ε⊥) in the minor axis direction of the liquid crystal molecules was measured. The value of dielectric anisotropy was calculated from the equation: Δε = ε∥−ε⊥.
[Example 1]

Synthesis of compound (1-2)

First Step: Compound (T-1) (Apollo Scientific) (25.0 g) and acetonitrile (450 ml) were added to a reactor under a nitrogen atmosphere, and sodium dithinite (7.83 g) and sodium hydrogen carbonate. An aqueous solution in which (3.21 g) was dissolved in water (65 ml) was slowly added dropwise, and the mixture was further stirred for 10 minutes. Subsequently, the reaction solution was cooled to 0 ° C., and a mixed solution of 1-pentene (4.19 ml) and acetonitrile (40 ml) was slowly added dropwise and stirred for 30 minutes. The obtained reaction mixture was poured into ice water, and the aqueous layer was extracted with heptane. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by column chromatography (silica gel; heptane) to obtain compound (T-2) (8.88 g; 32%).

Second Step Compound (T-2) (8.88 g), allyl bromide (1.14 ml), and acetonitrile (240 ml) were added to a reactor under a nitrogen atmosphere and cooled to 0 ° C. Thereto was slowly added dropwise an aqueous solution prepared by dissolving sodium dithinite (6.28 g) and sodium hydrogen carbonate (2.58 g) in water (60 ml), and the mixture was further stirred for 2 hours. The obtained reaction mixture was poured into ice water, and the aqueous layer was extracted with heptane. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by column chromatography (silica gel; heptane) to obtain compound (T-3) (4.46 g; 57%).

Step 3 Compound (T-3) (4.46 g), sodium hydrogen carbonate (0.542 g), Raney nickel (0.223 g), and methanol (20 ml) are added to the reactor, and the mixture is stirred under a hydrogen atmosphere for 12 hours. did. After the catalyst was filtered off, the resulting reaction mixture was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by column chromatography (silica gel; heptane). Furthermore, it refine | purified by recrystallization from Solmix A-11 (registered trademark; Japan Alcohol Sales Co., Ltd.), and the compound (1-2) (2.19 g; 61%) was obtained.

Chemical shift δ (ppm; CDCl ₃ ); 2.12-1.95 (m, 4H), 1.70-1.55 (m, 4H), 1.42-1.28 (m, 4H), 1 .03 (t, J = 7.40 Hz, 3H), 0.92 (t, J = 6.80 Hz, 3H).

The phase transition temperature of compound (1-2) was as follows.
Phase transition temperature: C 2.2 _S B 26.8 I.
[Example 2]
Physical properties of compound (1-2)

  A composition B composed of 90% by weight of the mother liquid crystal A and 10% by weight of the compound (1-2) obtained in Example 1 was prepared. The physical property value of the compound (1-2) was computed by measuring the physical property of the obtained composition B and extrapolating the measured value. The results were as follows.

Maximum temperature (T _NI ) = − 8.9 ° C .; dielectric anisotropy (Δε) = 0.10; refractive index anisotropy (Δn) = 0.053; viscosity (η) = − 2.1 mPa · s .

From these facts, it was found that the compound (1-2) was a compound having a liquid crystal phase, a high maximum temperature, and a low viscosity although it was a compound having no ring structure.
[Example 3]

Synthesis of compound (1-4)

Step 1 Using 1-heptene instead of 1-pentene, Compound (T-4) (9.82 g; 34%) was obtained in the same manner as in the synthesis of Compound (T-2) of Example 1. .

Step 2 Compound (T-5) (4.75 g; 55%) was prepared in the same manner as in the synthesis of Compound (T-3) of Example 1 using Compound (T-4) (9.82 g) as a starting material. )

Step 3 Compound (1-4) (2.52 g; 65%) was prepared in the same manner as in the synthesis of Compound (1-2) of Example 1 using Compound (T-5) (4.75 g) as a raw material. )

Chemical shift δ (ppm; CDCl ₃ ); 2.11-1.95 (m, 4H), 1.70-1.51 (m, 4H), 1.42-1.21 (m, 8H), 1 .03 (t, J = 7.25 Hz, 3H), 0.89 (t, J = 6.65 Hz, 3H).

The phase transition temperature of compound (1-4) was as follows.
Phase transition _{temperature: C 1 -0.2 C 2 10.0 S} B 32.5 I.
[Example 4]

Physical properties of compound (1-4) A composition C consisting of 85% by weight of the mother liquid crystal A and 15% by weight of the compound (1-4) obtained in Example 3 was prepared. The physical property value of the compound (1-4) was computed by measuring the physical property of the obtained composition C and extrapolating the measured value. The results were as follows.

Maximum temperature (T _NI ) = − 6.6 ° C .; dielectric anisotropy (Δε) = − 0.23; refractive index anisotropy (Δn) = 0.046; viscosity (η) = 1.9 mPa · s .

From these facts, it was found that the compound (1-4) was a compound having a liquid crystal phase, a high maximum temperature and a low viscosity even though it was a compound having no ring structure.
[Example 5]

Synthesis of compound (1-34)

First Step Compound (T-4) (8.85 g), allyl alcohol (1.21 ml), and acetonitrile (200 ml) were added to a reactor under a nitrogen atmosphere and cooled to 0 ° C. Thereto was slowly added dropwise an aqueous solution prepared by dissolving sodium dithionite (3.62 g) and sodium hydrogen carbonate (1.48 g) in water (50 ml), and the mixture was further stirred for 2 hours while returning to room temperature. The obtained reaction mixture was poured into ice water, and the aqueous layer was extracted with heptane. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by column chromatography (silica gel; toluene / ethyl acetate (= 10/1 (volume ratio))) to obtain compound (T-6) (6.37 g; 67% )

Second Step Lithium aluminum hydride (1.05 g) and tetrahydrofuran (THF) (120 ml) were added to the reactor under a nitrogen atmosphere and cooled to −10 ° C. Thereto was slowly added dropwise a solution prepared by dissolving compound (T-6) (6.37 g) in THF (30 ml), and the mixture was further stirred for 12 hours while returning to room temperature. The obtained reaction mixture was poured into a saturated aqueous ammonium chloride solution, insolubles were filtered off, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by column chromatography (silica gel; toluene / ethyl acetate (= 10/1 (volume ratio))) to obtain compound (T-7) (3.48 g; 79% )

Step 3 Compound (T-7) (3.48 g) and dichloromethane (70 ml) were added to a reactor under a nitrogen atmosphere and cooled to 0 ° C. To this, desmartin periodinane (2.91 g) was slowly added, and the mixture was further stirred for 1 hour while returning to room temperature. The insoluble material was filtered off, and the obtained solution was concentrated under reduced pressure. The residue was purified by column chromatography (silica gel; toluene) to obtain compound (T-8) (3.27 g; 94%). It was.

Fourth Step Methyltriphenylphosphonium bromide (2.52 g) and THF (40 ml) were added to a reactor under a nitrogen atmosphere, and the mixture was cooled to -30 ° C. A solution prepared by dissolving potassium-t-butoxide (0.759 g) in THF (10 ml) was slowly added thereto, and the mixture was further stirred for 30 minutes. Subsequently, a solution of compound (T-8) (3.27 g) in THF (15 ml) was slowly added, and the mixture was further stirred for 1 hour while returning to room temperature. The obtained reaction mixture was poured into ice water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed successively with 1N hydrochloric acid, a saturated aqueous sodium hydrogen carbonate solution and water, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by column chromatography (silica gel; heptane). Further purification by recrystallization from Solmix A-11 gave compound (1-34) (1.17 g; 36%).

Chemical shift δ (ppm; CDCl ₃ ); 5.83 (ddt, J = 16.8 Hz, J = 10.4 Hz, J = 6.50 Hz, 1H), 5.12 (dd, J = 17.0 Hz, J = 1.25 Hz, 1H), 5.07 (d, J = 10.2 Hz, 1H), 2.42-2.33 (m, 2H), 2.24-1.98 (m, 4H), 1 .64-1.55 (m, 2H), 1.42-1.23 (m, 8H), 0.89 (t, J = 6.75 Hz, 3H).

The phase transition temperature of compound (1-34) was as follows.
Phase transition temperature: C 21.9 S _B 35.0 I.
[Example 6]

Physical Properties of Compound (1-34) Composition D comprising 85% by weight of mother liquid crystals A and 15% by weight of compound (1-34) obtained in Example 5 was prepared. The physical property value of the compound (1-34) was computed by measuring the physical property of the obtained composition D and extrapolating the measured value. The results were as follows.

Maximum temperature (T _NI ) = − 7.9 ° C .; dielectric anisotropy (Δ∈) = 0.43; refractive index anisotropy (Δn) = 0.046; viscosity (η) = 6.0 mPa · s.

From these results, it was found that the compound (1-34) was a compound having a liquid crystal phase, a high maximum temperature, and a low viscosity although it was a compound having no ring structure.
[Example 7]

Synthesis of compound (1-44)

First Step: Lithium aluminum hydride (0.240 g) and THF (40 ml) were added to a reactor under a nitrogen atmosphere and cooled to −10 ° C. Thereto was slowly added a solution of compound (T-5) (3.50 g) in THF (10 ml), and the mixture was stirred for 12 hours while returning to room temperature. The obtained reaction mixture was poured into a saturated aqueous ammonium chloride solution, insolubles were filtered off, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by column chromatography (silica gel; heptane) to obtain compound (1-44) (1.32 g; 46%).

Chemical shift δ (ppm; CDCl ₃ ); 5.81 (ddt, J = 17.1 Hz, J = 10.2 Hz, J = 7.00 Hz, 1H), 5.38-5.30 (m, 2H), 2.86 (td, J = 18.3 Hz, J = 6.95 Hz, 2H), 2.05 (tt, J = 18.7 Hz, J = 8.15 Hz, 2H), 1.64-1.55 ( m, 2H), 1.42-1.23 (m, 8H), 0.89 (t, J = 7.05 Hz, 3H).

The phase transition temperature of compound (1-44) was as follows.
Phase transition temperature: C 1.3 _S B 24.4 I.
[Example 8]

Physical property of compound (1-44) Composition E composed of 85% by weight of mother liquid crystals A and 15% by weight of compound (1-44) obtained in Example 7 was prepared. The physical property value of the compound (1-44) was computed by measuring the physical property of the obtained composition E and extrapolating the measured value. The results were as follows.

Maximum temperature (T _NI ) = − 13.2 ° C .; dielectric anisotropy (Δε) = − 0.23; refractive index anisotropy (Δn) = 0.046; viscosity (η) = − 0.7 mPa · s.

From these results, it was found that the compound (1-44) was a compound having a liquid crystal phase, a high maximum temperature, and a low viscosity although it was a compound having no ring structure.
[Example 9]

Synthesis of compound (1-62)

First Step Compound (T-1) (25.0 g), allyl alcohol (2.61 ml), and acetonitrile (750 ml) were added to a reactor under a nitrogen atmosphere, and sodium dithinite (4.03 g) and carbonic acid were added. An aqueous solution in which sodium hydrogen (1.61 g) was dissolved in water (50 ml) was slowly added dropwise and stirred for 3 hours. Subsequently, allyl bromide (3.23 ml) was added, and an aqueous solution obtained by dissolving sodium dithionite (8.06 g) and sodium hydrogen carbonate (3.21 g) in water (100 ml) was slowly added dropwise, and further for 2 hours. Stir. The obtained reaction mixture was poured into ice water, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by column chromatography (silica gel; toluene / ethyl acetate (= 10/1 (volume ratio))) to obtain compound (T-9) (4.82 g; 20% )

Second Step Lithium aluminum hydride (0.730 g) and THF (80 ml) were added to a reactor under a nitrogen atmosphere and cooled to −10 ° C. A solution of compound (T-9) (4.82 g) in THF (20 ml) was slowly added dropwise thereto, and the mixture was further stirred for 12 hours while returning to room temperature. The obtained reaction mixture was poured into a saturated aqueous ammonium chloride solution, insolubles were filtered off, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by column chromatography (silica gel; toluene / ethyl acetate (= 3/1 (volume ratio))) to obtain compound (T-11) (3.44 g; 89% )

Step 3 Compound (T-11) (3.14 g; 92%) was prepared in the same manner as in the synthesis of Compound (T-8) of Example 5 using Compound (T-10) (3.44 g) as a starting material. )

Step 4 Compound (1-62) (0.700 g; 22%) was prepared in the same manner as in the synthesis of Compound (1-34) of Example 5 using Compound (T-11) (3.14 g) as a starting material. )

Chemical shift δ (ppm; CDCl ₃ ); 5.89-5.75 (m, 2H), 5.38-5.30 (m, 2H), 5.16-5.04 (m, 2H), 2 .86 (td, J = 18.3 Hz, 6.95 Hz, 2H), 2.41-2.32 (m, 2H), 2.25-2.10 (m, 2H).

The phase transition temperature of compound (1-62) was as follows.
Phase transition temperature: C -29.8 S _B -5.1 I.
[Example 10]
Physical properties of compound (1-62)

  A composition F consisting of 85% by weight of the base liquid crystal A and 15% by weight of the compound (1-62) obtained in Example 9 was prepared. The physical property value of the compound (1-62) was computed by measuring the physical property of the obtained composition F and extrapolating the measured value. The results were as follows.

Maximum temperature (T _NI ) = − 20.6 ° C .; dielectric anisotropy (Δε) = 0.43; refractive index anisotropy (Δn) = 0.046; viscosity (η) = − 11.7 mPa · s .

From these facts, it was found that the compound (1-62) was a compound having a liquid crystal phase and a particularly low viscosity even though it was a compound having no ring structure.
[Example 11]

Synthesis of compound (1-71)

Step 1 Compound (T-1) (25.0 g), allyl alcohol (5.75 ml), and acetonitrile (750 ml) are added to a reactor under a nitrogen atmosphere, and sodium dithinite (8.88 g) and carbonic acid are added. An aqueous solution in which sodium hydrogen (3.21 g) was dissolved in water (100 ml) was slowly added dropwise and stirred for 2 hours. The obtained reaction mixture was poured into ice water, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by column chromatography (silica gel; toluene / ethyl acetate (= 3/1 (volume ratio))) to obtain compound (T-12) (24.0 g; 82% )

Second Step Lithium aluminum hydride (5.32 g) and THF (240 ml) were added to a reactor under a nitrogen atmosphere and cooled to −10 ° C. A solution prepared by dissolving the compound (T-12) (24.0 g) in THF (120 ml) was slowly added dropwise thereto, and the mixture was further stirred for 12 hours while returning to room temperature. The obtained reaction mixture was poured into a saturated aqueous ammonium chloride solution, insolubles were filtered off, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by recrystallization from toluene to obtain Compound (T-13) (13.2 g; 81%).

Step 3 Compound (T-13) (4.00 g) and dichloromethane (80 ml) were added to a reactor under a nitrogen atmosphere, and the mixture was cooled to 0 ° C. Thereto, desmartin periodinane (6.87 g) was slowly added, and the mixture was further stirred for 1 hour while returning to room temperature. The insoluble material was filtered off, the obtained solution was concentrated under reduced pressure, and the residue was purified by column chromatography (silica gel; toluene / ethyl acetate (= 20/1 (volume ratio))) to obtain the compound (T -14) (2.95 g; 74%).

Fourth Step Methyltriphenylphosphonium bromide (4.92 g) and THF (55 ml) were added to a reactor under a nitrogen atmosphere and cooled to −30 ° C. Thereto, potassium-t-butoxide (1.42 g) was slowly added, and the mixture was further stirred for 30 minutes. Subsequently, a solution of compound (T-14) (2.95 g) dissolved in THF (20 ml) was slowly added, and the mixture was further stirred for 1 hour while returning to room temperature. The obtained reaction mixture was poured into ice water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed successively with 1N hydrochloric acid, a saturated aqueous sodium hydrogen carbonate solution and water, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by column chromatography (silica gel; heptane). Further purification by recrystallization from Solmix A-11 gave compound (1-71) (0.760 g; 26%).

Chemical shift δ (ppm; CDCl ₃ ); 5.83 (ddt, J = 17.0 Hz, J = 10.4 Hz, J = 6.50 Hz, 2H), 5.17-5.05 (m, 4H), 2.41-2.33 (m, 4H), 2.24-2.10 (m, 4H).

The phase transition temperature of compound (1-71) was as follows.
Phase transition temperature: C 21.4 (S _B 13.5) I.
[Example 12]
Physical properties of compound (1-71)

  A composition G consisting of 85% by weight of the base liquid crystal A and 15% by weight of the compound (1-71) obtained in Example 11 was prepared. The physical property value of the compound (1-71) was computed by measuring the physical property of the obtained composition G and extrapolating the measured value. The results were as follows.

Maximum temperature (T _NI ) = − 13.2 ° C .; dielectric anisotropy (Δ∈) = 0.43; refractive index anisotropy (Δn) = 0.046; viscosity (η) = − 13.2 mPa · s .

From these facts, it was found that the compound (1-71) was a compound having a liquid crystal phase, a high maximum temperature and a particularly low viscosity despite being a compound having no ring structure.
[Example 13]

Synthesis of compound (1-67)

First Step Compound (T-13) (21.2 g), THF (420 ml), and sodium hydride (1.96 g) were added to a reactor under a nitrogen atmosphere, and the mixture was stirred at 50 ° C. for 3 hours. Subsequently, the reaction solution was cooled to 0 ° C., triisopropylsilyl chloride (8.67 ml) was slowly added dropwise, and the mixture was further stirred for 12 hours. The obtained reaction mixture was poured into a saturated aqueous ammonium chloride solution, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by column chromatography (silica gel; toluene / ethyl acetate (= 5/1 (volume ratio))) to obtain compound (T-15) (13.9 g; 50% )

Step 2 Compound (T-16) (13.1 g; 95%) was prepared in the same manner as in the synthesis of Compound (T-8) of Example 5 using Compound (T-15) (13.9 g) as a starting material. )

Step 3 Compound (T-17) (9.14 g; 70%) was prepared in the same manner as in the synthesis of Compound (1-34) of Example 5 using Compound (T-16) (13.1 g) as a starting material. )

Step 4 Compound (T-17) (9.14 g) and THF (100 ml) were added to a reactor under a nitrogen atmosphere, and the mixture was cooled to 0 ° C. Tetrabutylammonium fluoride (1M; THF solution; 15.0 ml) was slowly added dropwise thereto and stirred for 12 hours while returning to room temperature. The obtained reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by column chromatography (silica gel; toluene / ethyl acetate (= 5/1 (volume ratio))) to obtain compound (T-18) (6.41 g; 91% )

Step 5 Compound (T-19) (2.89 g; 97%) was prepared in the same manner as in the synthesis of Compound (T-8) of Example 5 using Compound (T-18) (3.00 g) as a starting material. )

Step 6 To a reactor under a nitrogen atmosphere, compound (T-19) (2.89 g), 5-ethylsulfonyl-1-phenyl-1H-tetrazole (1.75 g), and ethylene glycol dimethyl ether (DME) (100 ml) ) And cooled to -70 ° C. To this, potassium hexamethyldisilazane (KHMDS) (1M; THF solution; 7.33 ml) was slowly added dropwise and stirred for 3 hours while returning to room temperature. The obtained reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by column chromatography (silica gel; heptane). Further purification by recrystallization from Solmix A-11 gave compound (1-67) (0.360 g; 12%).

Chemical shift δ (ppm; CDCl ₃ ); 5.83 (ddt, J = 17.0 Hz, J = 10.4 Hz, J = 6.45 Hz, 1H), 5.59-5.49 (m, 1H), 5.46-5.37 (m, 1H), 5.17-5.05 (m, 2H), 2.41-2.25 (m, 4H), 2.24-2.05 (m, 4H) ), 1.67 (dd, J = 6.35 Hz, J = 1.15 Hz, 3H).

The phase transition temperature of compound (1-67) was as follows.
Phase transition temperature: C 4.4 _S B 8.4 I.
[Example 14]
Physical properties of compound (1-67)

  A composition H consisting of 85% by weight of the base liquid crystal A and 15% by weight of the compound (1-67) obtained in Example 13 was prepared. The physical property value of the compound (1-67) was calculated by measuring the physical property of the obtained composition H and extrapolating the measured value. The results were as follows.

Maximum temperature (T _NI ) = − 16.4 ° C .; dielectric anisotropy (Δε) = 0.40; refractive index anisotropy (Δn) = 0.048; viscosity (η) = − 10.6 mPa · s .

From these facts, it was found that the compound (1-67) was a compound having a liquid crystal phase and a low viscosity even though the compound did not have a ring structure.
[Example 15]

Synthesis of compound (1-77)

Step 1 Compound (T-20) (10.6 g; 37%) was obtained by a method similar to the synthesis of compound (T-2) of Example 1 using 4-methylhexene instead of 1-pentene. It was.

Step 2 Compound (T-21) (4.43 g; 47%) was prepared in the same manner as in the synthesis of Compound (T-3) of Example 1 using Compound (T-20) (10.6 g) as a starting material. )

Step 3 Compound (1-77) (1.13 g; 31%) was prepared in the same manner as in the synthesis of compound (1-2) of Example 1 using compound (T-21) (4.43 g) as a starting material. )

Chemical shift δ (ppm; CDCl ₃ ); 2.12-1.95 (m, 4H), 1.70-1.50 (m, 4H), 1.42-1.30 (m, 3H), 1 .23-1.12 (m, 2H), 1.03 (t, J = 7.40 Hz, 3H), 0.87 (t, J = 6.50 Hz, 6H).

The phase transition temperature of compound (1-77) was as follows.
Phase transition temperature: C 24.8 I.
[Example 16]
Physical properties of compound (1-77)

  A composition I comprising 95% by weight of the mother liquid crystal A and 5% by weight of the compound (1-77) obtained in Example 15 was prepared. The physical property value of the compound (1-77) was computed by measuring the physical property of the obtained composition I and extrapolating the measured value. The results were as follows.

Maximum temperature (T _NI ) = − 23.9 ° C .; dielectric anisotropy (Δε) = − 0.80; refractive index anisotropy (Δn) = 0.033; viscosity (η) = 24.3 mPa · s .
[Example 17]

Based on Examples 1, 3, 5, 7, 9, 11, 13, 15 and the synthesis methods described above, compounds (1-1) to (1-100) shown below can be synthesized. In the description, R ¹ and R ² may be expressed in an inverted manner.

[Comparative Example 1]
As a comparative example, Mol. Cryst. Liq. Cryst. , 2006, 460, 63, the physical properties of the compound (S-1) were measured. In addition, the compound (S-1) used the commercial item (made by Matrix Scientific) as it was.

The phase transition temperature of the comparative compound (S-1) was as follows.
Phase transition temperature: C 16.9 S _B 36.7 I.

  A composition J consisting of 95% by weight of mother liquid crystal A and 5% by weight of comparative compound (S-1) was prepared. The physical property value of the comparative compound (S-1) was computed by measuring the physical property of the obtained composition J and extrapolating the measured value. The results were as follows.

Maximum temperature (T _NI ) = − 39.9 ° C .; dielectric anisotropy (Δε) = 1.10; refractive index anisotropy (Δn) = 0.013; viscosity (η) = 39.9 mPa · s.

  Comparative compound (S-1) and compounds (1-2), (1-4), (1-34), (1-44), (1-62), (1-67) shown in Examples (1-71) and (1-77) were compared. First, when comparing the compatibility, only (5%) of (S-1) could be added to the base liquid crystal A, whereas the compound (1-2) was 10% to the base liquid crystal A, and the compound ( 1-4), (1-34), (1-44), (1-62), (1-67), and (1-71) could be added to the mother liquid crystal A by 15%. Therefore, it was found that the compound of the present invention has better compatibility with other compounds and can be used even at lower temperatures.

Next, the comparative compound (S-1) and the compounds (1-2), (1-4), (1-34), (1-44), (1-62), (1-67), ( When comparing the maximum temperature (T _NI ) with 1-71) and (1-77), it was found that the compound of the present application had a higher T _NI . Therefore, it was found that the compound of the present invention is an excellent compound that can be used in a wide temperature range.

  Further, the comparative compound (S-1) and the compounds (1-2), (1-4), (1-34), (1-44), (1-62), (1-67), (1 When the viscosities of -71) and (1-77) were compared, these compounds of the present application had a lower viscosity. Therefore, it turned out that the direction of the compound of this invention is the outstanding viscosity reducing agent which can make the viscosity of a composition small.

Comparative compound (S-1) and compound (1-4) are both compounds having the same alkyl chain length and the same perfluoroalkyl chain length, but having an alkyl chain only at one end of the perfluoroalkyl chain. immediately, compatibility with other compounds is low, T _NI is low, the viscosity was greater. Therefore, it was difficult to use as a viscosity reducer for liquid crystal compositions, and it was found that introduction of alkyl chains at both ends of the perfluoroalkyl chain greatly contributed to the improvement of the properties of these compounds.

[Comparative Example 2]
Next, as a comparative example, a compound (S-3) described in DE 4034123 A1 was synthesized.

Chemical shift δ (ppm; CDCl ₃ ); 2.20-1.98 (m, 4H), 1.64-1.54 (m, 4H), 1.42-1.22 (m, 16H), 0 .94-0.86 (m, 6H).

The phase transition temperature of the comparative compound (S-3) was as follows.
Phase transition temperature: C 34.0 I.

  A composition K composed of 85% by weight of the base liquid crystal A and 15% by weight of the comparative compound (S-3) was prepared. The physical property of the obtained composition K was measured, and the extrapolated value of the physical property of the comparative compound (S-3) was calculated by extrapolating the measured value. The results were as follows.

Maximum temperature (T _NI ) = − 43.9 ° C .; dielectric anisotropy (Δε) = − 0.90; refractive index anisotropy (Δn) = 0.033; viscosity (η) = − 1.4 mPa · s.

  Comparative compound (S-3) and compounds (1-2), (1-4), (1-34), (1-44), (1-62), (1-67), (1-71 ) And (1-77), the compound (S-3) is a compound having no liquid crystal phase, whereas the compound (1-2), (1-4), ( 1-34), (1-44), (1-62), (1-67), and (1-71) were compounds having a liquid crystal phase. Therefore, it was found that the compound of the present invention is a superior compound as a constituent component of the liquid crystal composition.

Next, the comparative compound (S-3) and the compounds (1-2), (1-4), (1-34), (1-44), (1-62), (1-67), ( When comparing the maximum temperature (T _NI ) with 1-71) and (1-77), these compounds of the present application had higher T _NI . Therefore, it was found that the compound of the present invention is an excellent compound that can be used in a wide temperature range.

[Comparative Example 3]
Next, as a comparative example, a compound (S-4) described in DE10018086A1 was synthesized.

Chemical shift δ (ppm; CDCl ₃ ); 6.40 (dt, J = 15.7 Hz, J = 6.90 Hz, 2H), 5.59 (dt, J = 14.8 Hz, J = 12.5 Hz, 2H ),
2.25-2.15 (m, 4H), 1.50-1.40 (m, 4H), 1.40-1.25 (m, 6H), 0.95-0.87 (m, 6H) ).

The phase transition temperature of the comparative compound (S-4) was as follows.
Phase transition temperature: C <−50 I.

  A composition L composed of 85% by weight of the base liquid crystal A and 15% by weight of the comparative compound (S-4) was prepared. The physical property of the obtained composition L was measured, and the extrapolated value of the physical property of the comparative compound (S-4) was calculated by extrapolating the measured value. The results were as follows.

Maximum temperature (T _NI ) = − 98.6 ° C .; dielectric anisotropy (Δε) = − 1.47; refractive index anisotropy (Δn) = 0.013; viscosity (η) = 14.6 mPa · s .

  Comparative compound (S-4) and compounds (1-2), (1-4), (1-34), (1-44), (1-62), (1-67), (1-71 ) And (1-77), the compound (S-4) is a compound having no liquid crystal phase, whereas the compounds (1-2), (1-4), ( 1-34), (1-44), (1-62), (1-67), and (1-71) were compounds having a liquid crystal phase. Therefore, it was found that the compound of the present invention is a superior compound as a constituent component of the liquid crystal composition.

Next, the comparative compound (S-4) and the compounds (1-2), (1-4), (1-34), (1-44), (1-62), (1-67), ( When comparing the maximum temperature (T _NI ) with 1-71) and (1-77), these compounds of the present application had higher T _NI . Therefore, it was found that the compound of the present invention is an excellent compound that can be used in a wide temperature range.

  Further, the comparative compound (S-4) and the compounds (1-2), (1-4), (1-34), (1-44), (1-62), (1-67), (1 -71) and (1-77), the compounds (1-2), (1-4), (1-34), (1-44), (1-62) of the present application are compared. , (1-67), and (1-71) had lower viscosities. Therefore, it turned out that the direction of the compound of this invention is the outstanding viscosity reducing agent which can make the viscosity of a composition small.

[Comparative Example 4]
Further, a compound (S-5) described in DE10018086A1 was synthesized as a comparative example.

Chemical shift δ (ppm; CDCl ₃ ); 2.05 (tt, J = 18.8 Hz, J = 7.85 Hz, 4H), 1.65 to 1.56 (m, 4H), 1.43-1. 31 (m, 8H), 0.92 (t, J = 6.95 Hz, 6H).

The phase transition temperature of the comparative compound (S-5) was as follows.
Phase transition temperature: C ₁ 24.1 C ₂ 46.0 I.

  Comparative compound (S-5) and compounds (1-2), (1-4), (1-34), (1-44), (1-62), (1-67), (1-71 ) And (1-77), the compound (S-5) is a compound having no liquid crystal phase, whereas the compound (1-2), (1-4), ( 1-34), (1-44), (1-62), (1-67), and (1-71) were compounds having a liquid crystal phase. Therefore, it was found that the compound of the present invention is a superior compound as a constituent component of the liquid crystal composition.

The comparative compound (S-5) and the compound (1-4) are both compounds having the same molecular weight. However, when the alkyls at both ends are symmetrical, the melting point is improved as the crystallinity is improved and the liquid crystal phase is increased. Disappeared. That is, in the general formula (1) of the present invention, it has been found that the fact that R ¹ and R ² are not linear alkyl having the same carbon number greatly contributes to the development of the liquid crystal phase of the compound.
[Example 18]

Examples of Liquid Crystal Composition Examples of the liquid crystal composition obtained in the present invention will be described in detail below as composition examples. The liquid crystal compounds used in the composition examples are represented by symbols based on the definitions in the following table. In the table, 1,4-cyclohexylene has a trans configuration. The ratio (percentage) of each compound is a weight percentage (% by weight) based on the total weight of the composition unless otherwise specified. The characteristic of the composition obtained at the end of each composition example is shown.

  In addition, the number described in the portion of the liquid crystal compound used in each composition example corresponds to the formula number indicating the liquid crystal compound to be included in the liquid crystal composition of the present invention described above, and without describing the formula number, When only "-" is described, this compound means that it is another compound.

  The notation method by the symbol of a compound is shown below.

  The characteristics were measured according to the following method. Many of these are the methods described in the Standard of Electronic Industries Association of Japan EIAJ ED-2521A or a modified method thereof.

(1) Maximum temperature of nematic phase (NI; ° C)
A sample was placed on a hot plate of a melting point measurement apparatus equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature was measured when a part of the sample changed from a nematic phase to an isotropic liquid. Hereinafter, the upper limit temperature of the nematic phase may be abbreviated as “upper limit temperature”.

(2) Refractive index anisotropy (Δn; measured at 25 ° C.)
Measurement was performed using an Abbe refractometer with a polarizing plate attached to the eyepiece using light having a wavelength of 589 nm. First, after rubbing the surface of the main prism in one direction, the sample was dropped on the main prism. Then, the refractive index (n‖) when the polarization direction was parallel to the rubbing direction and the refractive index (n⊥) when the polarization direction was perpendicular to the rubbing direction were measured. The value of refractive index anisotropy (Δn) was calculated from the equation (Δn) = (n∥) − (n∥).

(3) Viscosity (bulk viscosity; η; measured at 20 ° C .; mPa · s)
An E-type viscometer was used for the measurement.

(4) Dielectric anisotropy (Δε; measured at 25 ° C.)
An ethanol (20 mL) solution of octadecyltriethoxysilane (0.16 mL) was applied to a well-cleaned glass substrate. The glass substrate was rotated with a spinner and then heated at 150 ° C. for 1 hour. A VA device having an interval (cell gap) of 20 μm was assembled from two glass substrates.

  In the same manner, a polyimide alignment film was prepared on a glass substrate. After the alignment film of the obtained glass substrate was rubbed, a TN device in which the distance between the two glass substrates was 9 μm and the twist angle was 80 degrees was assembled.

  A sample was put into the obtained VA device, 0.5 V (1 kHz, sine wave) was applied, and the dielectric constant (ε‖) in the major axis direction of the liquid crystal molecules was measured.

Further, a sample was put into the obtained TN device, 0.5 V (1 kHz, sine wave) was applied, and the dielectric constant (ε⊥) in the minor axis direction of the liquid crystal molecules was measured.
The value of dielectric anisotropy was calculated from the equation: Δε = ε∥−ε⊥.
A composition having a negative value is a composition having a negative dielectric anisotropy.

(5) Threshold voltage (Vth; measured at 25 ° C .; V)
(5-1) Composition having positive dielectric anisotropy: Normally white, in which the distance (gap) between two glass substrates is (0.5 / Δn) μm and the twist angle is 80 degrees A sample was put in a liquid crystal display element in a mode (normally white mode). Δn is a value of refractive index anisotropy measured by the above method. A rectangular wave having a frequency of 32 Hz was applied to this element. The voltage of the rectangular wave was increased and the value of the voltage when the transmittance of light passing through the element reached 90% was measured.

(5-2) Composition having a negative dielectric anisotropy: a normally black mode liquid crystal in which the distance (gap) between two glass substrates is about 9 μm and is processed in a homeotropic alignment A sample was put in the display element. A rectangular wave having a frequency of 32 Hz was applied to this element. The voltage of the rectangular wave was raised, and the value of the voltage when the transmittance of light passing through the element reached 10% was measured.

[Composition Example 1]
5-F8-3 (1-2) 5%
7-F8-3 (1-4) 5%

5-HB-CL (2-2) 16%
3-HH-4 (12-1) 12%
3-HH-5 (12-1) 4%
3-HHB-F (3-1) 4%
3-HHB-CL (3-1) 3%
4-HHB-CL (3-1) 4%
3-HHB (F) -F (3-2) 10%
5-HHB (F) -F (3-2) 8%
7-HHB (F) -F (3-2) 8%
5-HBB (F) -F (3-23) 4%
1O1-HBBH-5 (14-1) 3%
3-HHBB (F, F) -F (4-6) 2%
4-HHBB (F, F) -F (4-6) 3%
5-HHBB (F, F) -F (4-6) 3%
3-HH2BB (F, F) -F (4-15) 3%
4-HH2BB (F, F) -F (4-15) 3%
NI = 104.2 ° C .; Δn = 0.088; Δε = 3.2; Vth = 2.60 V; η = 17.3 mPa · s.

[Composition Example 2]
7-F8-1V (1-44) 5%
7-F8-2V (1-34) 4%

3-HHB (F, F) -F (3-3) 9%
3-H2HB (F, F) -F (3-15) 8%
4-H2HB (F, F) -F (3-15) 8%
5-H2HB (F, F) -F (3-15) 8%
3-HBB (F, F) -F (3-24) 21%
5-HBB (F, F) -F (3-24) 20%
3-H2BB (F, F) -F (3-27) 8%
5-HHBB (F, F) -F (4-6) 3%
5-HHEBB-F (4-17) 2%
1O1-HBBH-5 (14-1) 4%
NI = 80.6 ° C .; Δn = 0.106; Δε = 8.3; Vth = 1.48 V; η = 30.0 mPa · s.
When 0.25 part by weight of (Op-5) was added to 100 parts by weight of the composition, the pitch was 58.7 μm.

[Composition Example 3]
7-F8-1V (1-44) 3%
V2-F8-1V (1-62) 3%

5-HB-F (2-2) 12%
6-HB-F (2-2) 9%
7-HB-F (2-2) 7%
2-HHB-OCF3 (3-1) 7%
3-HHB-OCF3 (3-1) 7%
4-HHB-OCF3 (3-1) 7%
5-HHB-OCF3 (3-1) 5%
3-HH2B-OCF3 (3-4) 4%
5-HH2B-OCF3 (3-4) 4%
3-HHB (F, F) -OCHF2 (3-3) 4%
3-HHB (F, F) -OCF3 (3-3) 5%
3-HH2B (F) -F (3-5) 3%
3-HBB (F) -F (3-23) 7%
5-HBB (F) -F (3-23) 7%
5-HBBH-3 (14-1) 3%
3-HB (F) BH-3 (14-2) 3%
NI = 79.1 ° C .; Δn = 0.087; Δε = 4.0; Vth = 2.42 V; η = 12.6 mPa · s.

[Composition Example 4]
7-F8-2V (1-34) 4%
V2-F8-2V (1-71) 4%

5-HB-CL (2-2) 8%
3-HH-4 (12-1) 8%
3-HHB-1 (13-1) 2%
3-HHB (F, F) -F (3-3) 8%
3-HBB (F, F) -F (3-24) 20%
5-HBB (F, F) -F (3-24) 15%
3-HHEB (F, F) -F (3-12) 8%
4-HHEB (F, F) -F (3-12) 3%
5-HHEB (F, F) -F (3-12) 3%
2-HBEB (F, F) -F (3-39) 3%
3-HBEB (F, F) -F (3-39) 5%
5-HBEB (F, F) -F (3-39) 3%
3-HHBB (F, F) -F (4-6) 6%
NI = 72.6 ° C .; Δn = 0.100; Δε = 8.3; Vth = 1.40 V; η = 20.7 mPa · s.

[Composition Example 5]
7-F8-1V (1-44) 4%
1V2-F8-2V (1-67) 4%

3-HB-CL (2-2) 3%
5-HB-CL (2-2) 4%
3-HHB-OCF3 (3-1) 5%
3-H2HB-OCF3 (3-13) 5%
5-H4HB-OCF3 (3-19) 15%
V-HHB (F) -F (3-2) 5%
3-HHB (F) -F (3-2) 5%
5-HHB (F) -F (3-2) 5%
3-H4HB (F, F) -CF3 (3-21) 8%
5-H4HB (F, F) -CF3 (3-21) 10%
5-H2HB (F, F) -F (3-15) 5%
5-H4HB (F, F) -F (3-21) 7%
2-H2BB (F) -F (3-26) 5%
3-H2BB (F) -F (3-26) 5%
3-HBEB (F, F) -F (3-39) 5%
NI = 64.6 ° C .; Δn = 0.092; Δε = 7.7; Vth = 1.71 V; η = 23.7 mPa · s.

[Composition Example 6]
7-F8-1V (1-44) 5%
7-F8-V1 (1-54) 5%

5-HB-CL (2-2) 7%
7-HB (F, F) -F (2-4) 3%
3-HH-4 (12-1) 10%
3-HH-5 (12-1) 5%
3-HB-O2 (12-5) 15%
3-HHB-1 (13-1) 8%
3-HHB-O1 (13-1) 5%
2-HHB (F) -F (3-2) 7%
3-HHB (F) -F (3-2) 7%
5-HHB (F) -F (3-2) 7%
3-HHB (F, F) -F (3-3) 6%
3-H2HB (F, F) -F (3-15) 5%
4-H2HB (F, F) -F (3-15) 5%

[Composition Example 7]
7-F8-3 (1-4) 5%
7-F10-3 (1-81) 5%

5-HB-CL (2-2) 3%
7-HB (F) -F (2-3) 7%
3-HH-4 (12-1) 9%
3-HH-EMe (12-2) 23%
3-HHEB-F (3-10) 8%
5-HHEB-F (3-10) 8%
3-HHEB (F, F) -F (3-12) 10%
4-HHEB (F, F) -F (3-12) 5%
5-HGB (F, F) -F (3-103) 6%
2-H2GB (F, F) -F (3-106) 4%
5-GHB (F, F) -F (3-109) 7%

[Composition Example 8]
5-F8-3 (1-2) 5%
7-F8-3 (1-4) 5%

3-HB-O2 (12-5) 10%
5-HB-CL (2-2) 13%
3-HBB (F, F) -F (3-24) 7%
3-PyB (F) -F (2-15) 10%
5-PyB (F) -F (2-15) 10%
3-PyBB-F (3-80) 10%
4-PyBB-F (3-80) 10%
5-PyBB-F (3-80) 10%
5-HBB (F) B-3 (14-5) 10%
NI = 75.3 ° C .; Δn = 0.171; Δε = 7.6; Vth = 1.54 V; η = 33.9 mPa · s.

[Composition Example 9]
5-F8-3 (1-2) 4%
7-F8-3 (1-4) 3%

2-BEB (F) -C (5-14) 5%
3-BEB (F) -C (5-14) 4%
4-BEB (F) -C (5-14) 12%
1V2-BEB (F, F) -C (5-15) 12%
3-HB-O2 (12-5) 11%
2-HH-3 (12-1) 11%
3-HH-4 (12-1) 10%
3-HHB-1 (13-1) 8%
3-HHB-O1 (13-1) 4%
3-H2BTB-2 (13-17) 4%
3-H2BTB-3 (13-17) 4%
3-H2BTB-4 (13-17) 4%
3-HB (F) TB-2 (13-18) 4%
NI = 77.3 ° C .; Δn = 0.131; Δε = 14.8; Vth = 1.12 V; η = 21.0 mPa · s.

[Composition Example 10]
V2-F8-2V (1-71) 5%
1V2-F8-2V (1-67) 5%

2-HB-C (5-1) 6%
3-HB-C (5-2) 14%
2-BEB-C (5-13) 10%
3-HB-CL (2-2) 15%
3-HHB-CL (3-1) 7%
5-HHB-CL (3-1) 5%
3-HHB-F (3-1) 4%
3-HHEB-F (3-10) 3%
2-HHB (F) -F (3-2) 7%
3-HHB (F) -F (3-2) 7%
5-HHB (F) -F (3-2) 7%
3-HHB (F, F) -F (3-3) 5%
NI = 76.7 ° C .; Δn = 0.113; Δε = 8.1; Vth = 1.58 V; η = 18.2 mPa · s.

[Composition Example 11]
V2-F8-1V (1-62) 5%
7-F8-3 (1-4) 5%
7-F8-V1 (1-54) 5%
7-F10-3 (1-81) 5%

2-BB-C (5-5) 10%
5-BB-C (5-5) 10%
3-BEB-C (5-13) 12%
4-BEB-C (5-13) 12%
5-BEB-C (5-13) 12%
5-BBB-C (5-34) 7%
3-HHB-C (5-28) 7%
5-HHB-C (5-28) 10%

  The present invention provides a novel liquid crystal compound having a high clearing point, good compatibility with other compounds, small viscosity, and high stability against heat, light, and the like. In addition, a new liquid crystal composition having desirable characteristics is provided by appropriately selecting a terminal chain constituting the compound using the liquid crystal compound as a component. Furthermore, liquid crystal display elements using this liquid crystal composition can be widely used in displays such as watches, calculators and personal computers.

Claims (18)

The compound represented by Formula (1).

In Formula (1), R ¹ is alkyl having 4 to 10 carbons, — (CH ₂ ) ₂ —CH═CH ₂ , or — (CH ₂ ) ₂ —CH═CHCH ₃ , and R ² is ² carbons 10 _{alkyl, -CH = CH 2, -CH =} CHCH 3, -CH 2 CH = CH 2, -CH 2 CH = CHCH 3, - (CH 2) 2 -CH = CH 2 or, - (CH ₂ ) ₂ -CH = CHCH ₃ der Ri, n is 8, 9, 10, 11 or 12,, ^{R 1} ≠ ^{R 2} and is of compounds. In Formula (1), R ¹ is alkyl having 4 to 10 carbons, — (CH ₂ ) ₂ —CH═CH ₂ , or — (CH ₂ ) ₂ —CH═CHCH ₃ , and R ² is ² carbons 10 _{alkyl, -CH = CH 2, -CH =} CHCH 3, -CH 2 CH = CH 2, -CH 2 CH = CHCH 3, - (CH 2) 2 -CH = CH 2 or, - (CH ₂ ) ₂ -CH = CHCH is _3, n is 8, 9 or 10, the compound of claim 1 which is ^{R 1} ≠ ^{R 2.}
The compound according to claim 2 , wherein n is 8 in the formula (1) according to claim 1. In the formula (1) according to claim 1, ^{R 1} is alkyl of 4 to 10 carbon atoms, A compound according to claim 3 ^{R 2} is alkyl having 2 to 7 carbon atoms. In the formula (1) according to claim 1, ^{R 1} is alkyl of 4 to 10 carbon atoms, ^{R 2} is _{-CH = CH 2, -CH = CHCH} 3, -CH 2 CH = CH 2, -CH _{2 CH = CHCH 3, - (} CH 2) 2 -CH = CH 2 or, _{- (CH} 2) compounds according to 2 -CH = CHCH ₃ a is claim 3. In the formula (1) according to claim 1, ^{R 1} is _{- (CH 2) 2 -CH =} CH 2 _{or, - (CH 2) 2 -CH} = CHCH is _3, ^{R 2} is -CH = CH _{2 , -CH = CHCH 3, -CH 2} CH = CH 2, -CH 2 CH = CHCH 3, - (CH 2) 2 -CH = CH 2 or, _{- (CH} 2) according a 2 -CH = CHCH ₃ Item 4. The compound according to Item 3 . The liquid crystal composition containing at least one compound according to any one of claims 1-6. The liquid crystal composition according to claim 7 , further comprising at least one compound selected from the group of compounds represented by formulas (2) to (4).

In the formulas (2) to (4), R ³ is independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one hydrogen may be replaced by fluorine. Well, at least one —CH ₂ — may be replaced by —O—; X ¹ is fluorine, chlorine, —OCF ₃ , —OCHF ₂ , —CF ₃ , —CHF ₂ , —CH ₂ F, — CF ₌ CF 2, be -OCF ₂ CHF ₂ or -OCF ₂ CHFCF _3,; ring ^{A 1,} ring ^{A 2,} and ring ^{A 3} are independently 1,4-cyclohexylene, 1,3-dioxane - 2,5-diyl, pyrimidine-2,5-diyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phen Nylene, or 3,5-difluoro-1,4-phenylene; Z ¹ and Z ² are independently — (CH ₂ ) ₂ —, — (CH ₂ ) ₄ —, —COO—, —CF _2. O—, —OCF ₂ —, —CH═CH—, —C≡C—, —CH ₂ O—, or a single bond; L ¹ and L ² are independently hydrogen or fluorine. The liquid crystal composition according to claim 7 , further comprising at least one compound selected from the group of compounds represented by formula (5).

In Formula (5), R ⁴ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in alkyl and alkenyl, at least one hydrogen may be replaced with fluorine, and at least one — CH ₂ — may be replaced by —O—; X ² is —C≡N or —C≡C—C≡N; Ring B ¹ , Ring B ² , and Ring B ³ are independently 1,4-cyclohexylene, 1,4-phenylene, 1,3-dioxane-2,5-diyl, tetrahydropyran-2,5-diyl, or pyrimidine-2 in which at least one hydrogen may be replaced by fluorine Z ³ is — (CH ₂ ) ₂ —, —COO—, —CF ₂ O—, —OCF ₂ —, —C≡C—, —CH ₂ O—, or a single bond Yes; L ³ and L ⁴ Is independently hydrogen or fluorine; r is 0, 1 or 2, s is 0 or 1, and the sum of r and s is 0, 1, 2 or 3. The liquid crystal composition according to claim 7 , further comprising at least one compound selected from the group of compounds represented by formulas (6) to (11).

In the formulas (6) to (11), R ⁵ and R ⁶ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one hydrogen is fluorine. And at least one —CH ₂ — may be replaced by —O—; Ring C ¹ , Ring C ² , Ring C ³ , and Ring C ⁴ are independently 1,4-cyclohex Silene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, tetrahydropyran-3,6-diyl, or decahydro-2 in which at least one hydrogen may be replaced by fluorine , be a ^{6-naphthalene; Z 4, Z 5, Z} 6, and ^{Z 7} are _{independently, - (CH 2) 2 -} , - COO -, - CH 2 O -, - OCF 2 -, _{OCF 2 (CH 2) 2 -} , or a single bond; ^{L 5} and ^{L 6} are independently fluorine or chlorine; t, u, v, w , x, and y are independently 0 or 1 And the sum of u, v, w, and x is 1 or 2. The liquid crystal composition according to claim 7 , further comprising at least one compound selected from the group of compounds represented by formulas (12) to (14).

In the formulas (12) to (14), R ⁷ and R ⁸ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH ₂ -May be replaced by -O-; Ring D ¹ , Ring D ² , and Ring D ³ are independently 1,4-cyclohexylene, pyrimidine-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z ⁸ and Z ⁹ are independently —C≡C— _{, -COO -, - (CH 2} ) 2 -, - CH = CH-, or a single bond. The liquid crystal composition according to claim 8 , further comprising at least one compound selected from the group of compounds represented by formula (5) according to claim 9 . Claim 1 1 wherein (12) according to (14) The liquid crystal composition according to claim 8, further comprising at least one compound selected from the group of compounds represented by. Claim 1 1 wherein (12) according to (14) The liquid crystal composition according to claim 9, further comprising at least one compound selected from the group of compounds represented by. Claim 1 1 wherein (12) according to (14) The liquid crystal composition according to claim 1 0, further comprising at least one compound selected from the group of compounds represented by. The liquid crystal composition according to any one of claims 7 to 15 , further comprising at least one optically active compound. The liquid crystal composition according to any one of claims 7 to 16 , further comprising at least one antioxidant and / or ultraviolet absorber. A liquid crystal display device containing the liquid crystal composition according to any one of claims 7-1 7.